JP2873850B2 - Processing method of silver halide color photographic light-sensitive material - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a bleaching solution for a silver halide color photographic light-sensitive material and a processing method using the bleaching solution, and more particularly to a halogenation in which bleaching fog is effectively prevented. The present invention relates to a method for processing a silver color photographic light-sensitive material.

[Background of the Invention]

Processing of the photosensitive material basically comprises two steps of color development and desilvering, and desilvering comprises a bleaching and fixing step or a bleach-fixing step. In addition, rinsing processing, stabilization processing, and the like are added as additional processing steps.

Processing solutions having a bleaching ability used in the desilvering step of silver halide color photographic light-sensitive materials widely use inorganic oxidizing agents such as red blood salts and dichromates as oxidizing agents for bleaching image silver. Was used.

However, processing solutions having bleaching ability containing these inorganic oxidizing agents have been pointed out with some serious drawbacks. For example, red blood salts and dichromates are relatively good in terms of the bleaching power of image silver, but can decompose by light to form harmful cyan ions and hexavalent chromium ions, causing pollution. It has unfavorable properties for prevention. Further, the processing liquid containing these inorganic oxidizing agents has a drawback that it is difficult to recycle the processing liquid without discarding the waste liquid after the processing.

On the other hand, there are few pollution problems,
In order to meet the demand for simplification and reusability of waste liquids, treatment liquids using an organic acid metal complex such as an aminopolycarboxylic acid metal complex as an oxidizing agent have come to be used. However, a processing solution using a metal complex salt of an organic acid has a drawback that the bleaching speed (oxidation speed) of image silver (metal silver) formed in the developing step is slow because of the slow oxidizing power. . For example, iron (III) ethylenediaminetetraacetate complex, which is considered to have strong bleaching power among aminopolycarboxylic acid metal complex salts, has been partially used as a bleaching solution and a bleach-fixing solution. High-sensitivity silver halide color photographic materials mainly composed of silver bromide, silver chlorobromide, and silver iodobromide emulsions, especially color papers for photography containing silver iodide as silver halide and having a high silver content, and For color negative films and color reversal films,
It has the disadvantage that the bleaching power is insufficient and the bleaching step requires a long time.

In a developing method in which a large amount of silver halide photographic light-sensitive material is continuously processed by an automatic processor or the like, in order to avoid deterioration in the performance of the bleaching solution due to a change in the component concentration, the components of the processing solution are kept within a certain concentration. Means are needed to keep In recent years, from the viewpoints of economy and pollution, a so-called concentrated low replenishment method in which these replenishers are concentrated and replenished in a small amount, or a method in which a regenerating agent is added to an overflow and used again as a replenisher has been proposed as such means. Is coming. In particular, in the bleaching solution, a ferrous organic acid complex formed by bleaching developed silver, for example, an iron (II) complex of ethylenediaminetetraacetate by aeration is used to form a complex of iron (III) ethylenediaminetetraacetate, ie, a ferric organic acid complex. A method has been put to practical use in which a regenerating agent for supplementing the deficient components is further added by oxidizing and returning the solution, and then used again as a replenisher.

However, in recent years, so-called compact labs (also known as mini labs) have emerged in order to shorten the processing time of silver halide color photographic light-sensitive materials and reduce collection and delivery costs.
In such a lab, there is a strong need for simplification of the processing and reduction in the installation area of the developing machine, which requires cumbersome labor and management, and regenerating processing that requires a processing space is not preferable.

Therefore, a rich low replenishment method in which low replenishment is performed without performing regenerating processing is preferable.However, when the replenishment amount of the bleaching solution is extremely reduced, the concentration of the color developing solution component brought into the bleaching solution increases, and concentration by evaporation is performed. And the accumulation of color developing solution components is further increased. As described above, when the concentration of the color developing solution component in the bleaching solution increases, the mixing ratio of the color developing agent and the sulfite, which are the reducing components, increases, and the bleaching reaction is suppressed. Disadvantageously occurs.

This bleaching fog is emphasized in the recent replenishment of the bleaching solution, and tends to cause a failure in which tar is generated in a bleaching tank of an automatic processor.

However, in recent years, the demand for lower pollution and lower costs has led to a demand for even lower replenishment. It has been required to carry out in the compact lab where the renewal rate of the tank liquid is very low. Under such circumstances, the above problems are becoming more and more serious.

[Object of the invention]

Accordingly, a first object of the present invention is to provide a method for processing a silver halide color photographic light-sensitive material having improved bleaching fog while allowing quick and low replenishment.

A second object of the present invention is to provide a method for processing a silver halide color photographic light-sensitive material having excellent processing stability and capable of performing both continuous processing and small amount processing over a long period of time.

[Configuration of the invention]

The object of the present invention is to provide a method for processing a silver halide color photographic light-sensitive material, which comprises treating a silver halide color photographic light-sensitive material with a color developer after imagewise exposure, and then immediately processing with a bleaching solution. The bleaching solution contains at least 0.10% of a ferric complex salt of a compound represented by the following general formula [A], wherein ammonium ion is 50 mol% or less of all cations.
This is achieved by a method for processing a silver halide color photographic light-sensitive material containing 1 mol / l and the replenishment amount of the bleaching solution is ^{20 to} 400 ml per 1 m2 of the silver halide color photographic light-sensitive material.

In the formula, A _{1 to} A ₄ may be the same or different,
CH ₂ OH, represents a -COOM or -PO ₃ M ₁ M _2. M, M ₁ and M ₂ each represent a hydrogen atom, sodium, potassium or ammonium. X represents a substituted or unsubstituted alkylene group having 3 to 6 carbon atoms.

A preferred embodiment is a method for processing a silver halide color photographic light-sensitive material in which the pH of the bleaching solution is 2.0 to 5.5, and a processing method in which the bleaching solution has an ammonium ion content of 20 mol% or less of all cations is also preferable. It is an embodiment.

In the present invention, the second compound represented by the general formula [A]
A bleaching solution containing an iron complex salt is known in JP-A-62-222252 and the like, and it is also known in the publication that bleaching fog is easily generated. It is also known, for example, in JP-A-2-44352 that the bleaching solution can be prevented by adjusting the pH of the bleaching solution to 2.5 to 5.5 in order to prevent fog. However, in the above-mentioned known examples, bleaching fog cannot be completely prevented by lowering the pH of the bleaching solution, and when the bleaching solution is replenished at a low level, or even when the processing amount is small, bleaching fog may not occur. It becomes even more noticeable.

The present invention has found that the bleaching fog is easily generated by the bleaching power of the ferric complex of the general formula [A], but the bleaching fog is more likely to be generated by using ammonium ions in the ferric complex. Thus, the present invention has been completed.

[Specific configuration of the invention]

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

A _{1 to} A ₄ may be the same or different, and
₂ OH, represents -COOM or -PO ₃ M ₁ M _2, represents M, M _1, M ₂ are each a hydrogen atom, sodium, potassium or ammonium. X represents a substituted or unsubstituted alkylene group having 3 to 6 carbon atoms (eg, propylene, butylene, pentamethylene, etc.).

Examples of the substituent include a hydroxyl group. Preferred specific examples of the compound represented by the general formula [A] are shown below.

As the compounds (A-1) to (A-9), besides the above, sodium salts, potassium salts or ammonium salts thereof can be used arbitrarily. However, if the amount of ammonium salts is large, bleaching fog tends to occur. More preferably, the content of the ammonium salt of the ferric complex is 50 mol% or less, preferably 20 mol% or less, and more preferably 0 to 10 mol%, from the viewpoint of preventing bleaching fog.

Among the above-mentioned compound examples, those particularly preferably used in the present invention include (A-1), (A-4) and (A-
7) and (A-8), and particularly preferred is (A-1).

The ferric complex salt of the compound represented by the general formula [A] is used in an amount of at least 0.10 mol per bleaching solution, preferably in the range of 0.15 mol to 0.6 mol, more preferably
The range is from 0.18 mol to 0.5 mol.

In the bleaching solution of the present invention, a ferric complex salt of the compound represented by the general formula [A] may be added to another ferric complex salt of an aminopolycarboxylic acid (for example, a ferric complex salt of ethylenediaminetetraacetic acid, a diethylenetriaminepentaacetic acid salt). Diiron complex salt, 1,2-cyclohexanediaminetetraacetic acid ferric complex salt, glycol ether diaminetetraacetic acid ferric complex salt, etc.) can be used in combination.

However, a bleaching solution containing substantially only a ferric complex salt of the compound represented by the above general formula [A] is preferable from the viewpoint of better achieving the effects of the present invention. Here, “substantially” means at least 70% (in terms of mol) or more of all ferric complex salts. The ratio is preferably at least 80%, more preferably at least 90%, most preferably at least 95%.

When the bleaching solution according to the present invention contains at least one of imidazole and its derivatives or the compounds represented by the following general formulas (I) to (IX), the bleaching solution exhibits the desired effects of the present invention more favorably. Since there is another effect of also improving the precipitation caused by silver in the bleaching solution, in the present invention,
More preferably used.

[In the formula, Q represents an atomic group necessary for forming a nitrogen-containing heterocyclic ring (including a condensed 5- to 6-membered unsaturated ring), and R ₁ represents a hydrogen atom, a carbon atom number of 1 to 1. 6 alkyl groups,
Represents a cycloalkyl group, an aryl group, a heterocyclic group (including those in which a 5- to 6-membered unsaturated ring is condensed), or an amino group. ] [In the formula, R ₂ and R ₃ each represent a hydrogen atom and a carbon atom 1
Represents an alkyl group, a hydroxy group, a carboxy group, an amino group, an acyl group having 1 to 3 carbon atoms, an aryl group or an alkenyl group.

A is Or n ₁ monovalent heterocyclic residue represents (5-6 membered unsaturated ring including those condensed), X is = S, = O or =
NR ″, where R and R ′ are R ₂ and R _3, respectively.
X ′ is the same as X, Z is a hydrogen atom, an alkali metal atom, an ammonium group, an amino group, a nitrogen-containing heterocyclic residue, an alkyl group, M represents a divalent metal atom, R ″ represents a hydrogen atom,
Represents an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group, an aryl group, a heterocyclic residue (including a condensed 5 to 6-membered unsaturated ring) or an amino group, and n _{1 to} n ₆ And m _{1 to} m ₅ each represent an integer of 1 to 6.

B represents an alkylene group having 1 to 6 carbon atoms, Wherein R ₄ and R ₅ have the same meanings as R ₂ and R ₃ , respectively. However, each of R ₄ and R ₅ may represent -B-SZ, also R ₂ and R _3, R and R ', R ₄ and R ₅ may each fused to form a ring.

The compound represented by the formula also includes an enol compound and a salt thereof. ] [Wherein, R ₆ and R ₇ are each a hydrogen atom and a carbon atom 1
6 alkyl group, hydroxy group, carboxy group, amino group, acyl group having 1 to 3 carbon atoms, an aryl group, an alkenyl group or -B ₁ -S-Z _1. However, R ₆ and R ₇ may combine to form a ring.

And B ₁ represents an alkylene group having 1 to 6 carbon atoms,
Z ₁ is a hydrogen atom, an alkali metal atom, an ammonium group, an amino group, a nitrogen-containing heterocyclic residue or Represents

n ₇ represents an integer of 1-6.

 General formula (IV)(Where R₈And R₉RespectivelyAnd R_TenIs an alkyl group or-(CH_Two) N₈SO_Three The table
You. (However, R_TenIs-(CH_Two) N₈SO_Three When l is 0
And represents 1 when it is an alkyl group. ) G Represents an anion. n₈Represents an integer of 1 to 6. ](Where Q₁Is a nitrogen-containing heterocycle (5- to 6-membered unsaturated ring or
Is necessary to form a compound having a condensed saturated ring)
Atom group, R₁₁Is a hydrogen atom, an alkali metal atom,Or represents an alkyl group. Where Q 'is Q₁Synonymous with
You. ](Where D₁, D_Two, D_ThreeAnd D_FourAre just unions
Hand, alkylene group having 1 to 8 carbon atoms or vinylene group
And q₁, Q_Two, Q_ThreeAnd q_FourAre 0, 1 or 2 respectively
Represents Further, the ring formed together with the sulfur atom is further 5 to
It may be fused with a 6-membered saturated or unsaturated ring. ](Where X_TwoIs -COOM ', -OH, -SO_ThreeM ′, − CONH_Two, −SO
_TwoNH_Two, -NH_Two, −SH, −CN, −CO_TwoR₁₆, −SO_TwoR₁₆, −O
R₁₆, −NR₁₆R₁₇, −SR₁₆, −SO_ThreeR₁₆, −NHCOR₁₆, −NHS
O_TwoR₁₆, −OCOR₁₆Or -SO_TwoR₁₆And Y_TwoIsOr a hydrogen atom, m₉And n₉Are 1 to 10 respectively
Represents an integer. R₁₁, R₁₂, R₁₃, R₁₄, R₁₅, R₁₇And R
₁₈Represents a hydrogen atom, a lower alkyl group, an acyl group,
OrAnd R₁₆Represents a lower alkyl group; R₁₉Is -NR₂₀R_{twenty one}, −OR
_{twenty two}Or -SR_{twenty two}And R₂₀And R_{twenty one}Is hydrogen
Represents an atom or a lower alkyl group, R_{twenty two}Is R₁₈Combined with
Represents the group of atoms necessary to form a ring. R₂₀Or R₁₁Is
R₁₈And may form a ring. M 'is a hydrogen atom
Or cation. ][Wherein, Ar is a divalent aryl group or an aryl group and oxygen
Divalent in combination with atoms and / or alkylene groups
Represents an organic group of B_TwoAnd B_ThreeAre low-grade
R_{twenty three}, R_{twenty four}, R_{twenty five}And R₂₆Are hidden
Represents a roxy-substituted lower alkyl group, wherein x and y are
Represents 0 or 1, respectively. G ′ represents an anion, and z is
Represents 0, 1 or 2. ](Where R₂₉And R₃₀Are hydrogen and alkyl
Group, an aryl group or a heterocyclic group, R₁₃Is hydrogen field
Represents an atom or an alkyl group, R₃₂Is a hydrogen atom or cal
Represents a boxy group. The compounds represented by the general formulas [I] to [IX] and imidazoles
Representative examples of dazole and its derivatives are described in Japanese Patent Application
No.-32501, page 17 to page 39, (I-
1) to (I-10), (II-1) to (II-27), (III-
1) to (III-15), (IV-1) to (IV-3), (V-
1) to (V-23), (VI-1) to (VI-17), (VII-
1) to (VII-15), (VIII-1) to (VIII-7), (I
X-1) to (IX-5) and (A-1) to (A-8).
Can be

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

These bleaching accelerators may be used alone or two or more of them may be used in combination.
Good results are obtained in the range of 0.01 to 100 g. However,
In general, when the amount added is too small, the bleach accelerating effect is small,
When the addition amount is excessively large, precipitation may occur to contaminate the silver halide color photographic light-sensitive material to be processed, so that it is preferably 0.05 to 50 g, more preferably 0.05 to 15 g per bleaching solution. is there.

When a bleaching accelerator is added, it may be added and dissolved as it is. However, it is general that the bleaching accelerator is dissolved in water, an alkali, an organic acid, or the like in advance, and then added, and if necessary, methanol, ethanol, acetone, etc. Can be added by dissolving using the above organic solvent.

The bleaching solution of the present invention can be used preferably at pH 2.0 to 5.5, more preferably at 3.0 to 5.0. If the pH of the bleaching solution is 5.5 or more, bleaching fog cannot be sufficiently prevented, and if the pH is 2 or less, bleaching fog is prevented but photographic performance may be affected. The temperature of the treatment is preferably used between 20 ° C and 45 ° C, more preferably between 25 ° C and 42 ° C.
° C.

In the bleaching solution of the present invention, a halide such as ammonium bromide is usually added and used.

The bleaching solution of the present invention comprises various salts such as boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, and ammonium hydroxide. pH
The buffer may be contained alone or in combination of two or more. Furthermore, various fluorescent whitening agents, defoaming agents, surfactants and deterrents can be added.

In the bleaching solution of the present invention, when the amount of ammonium ion is 50 mol% or less, preferably 20 mol%, particularly preferably 10 mol% or less of all cations, the bleaching fog which is the effect of the present invention is prevented.

Preferred replenishment rate of the bleaching solution according to the present invention is to not 20ml per silver halide color photographic light-sensitive material 1 m ² 400 ml,
Particularly preferably 30 ml to 350 ml, more particularly preferably 40 ml to 300 ml, most preferably 50 ml.
Or 250 ml.

The bleaching solution described above is preferably used immediately after color development during the processing step.

In the present invention, from the viewpoint of rapid processing, processing is preferably carried out with a fixing solution or a bleach-fixing solution after processing with a bleaching solution.

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

(1) Color development-bleaching-fixing-washing (2) Color development-bleaching-fixing-washing-stable (3) Color developing-bleaching-fixing-stable (4) Color developing-bleaching-fixing-first stable-first 2 Stable (5) Color development-Bleaching-Bleaching-Washing (6) Color development-Bleaching-Bleaching-Washing-Stable (7) Color development-Bleaching-Bleaching-Stable (8) Color development-Bleaching-Bleaching-fixing -1st stability-2nd stability Among these steps, (3), (4),
(6), (7) and (8) are preferred, and particularly (3), (4) and (7) are particularly preferred. Most preferably, it is (3).

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

As a fixing agent, a compound which reacts with silver halide to form a complex salt of an aqueous solution, for example, potassium thiosulfate, sodium thiosulfate, thiosulfates such as ammonium thiosulfate, potassium thiocyanate, sodium thiocyanate,
Thiocyanates such as ammonium thiocyanate, thiourea, thioether and the like are preferred, and thiosulfates and thiocyanates are preferred. In practicing the present invention, the ammonium ion of the fixing solution or the bleach-fixing solution is 50% or less, preferably 20% or less of the total cations as in the bleaching solution.
The following is a preferred embodiment, and it is effective to prevent stain although slightly.

In addition to these fixing agents, further fixing solutions and bleach-fixing solutions include ammonium sulfite, potassium sulfite, ammonium bisulfite, potassium bisulfite, sodium bisulfite,
Ammonium metabisulfite, potassium metabisulfite, sulfites such as sodium metabisulfite and boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid,
A pH buffer comprising various salts such as sodium acetate and ammonium hydroxide may be used alone or in combination of two or more.

Further alkali halide or ammonium halide,
For example, it is desirable to contain a large amount of a rehalogenating agent such as potassium bromide, sodium bromide, sodium chloride, and ammonium bromide. Borate, acid salt, acetate,
PH buffers such as carbonates and phosphates, alkylamines, polyethylene oxides and the like which are known to be added to ordinary fixing solutions and bleach-fixing solutions can be appropriately added.

The fixing agent is used as a fixing agent in an amount of 0.1 mol or more per processing solution, and is preferably used in view of the effects of the present invention.
0.3 mol to 4 mol, particularly preferably 0.5 mol to 3.0 mol.
It is particularly preferably used in the range of 0.6 mol to 2.0 mol.

In the present invention, air or oxygen may be blown in the processing bath and in the processing replenisher storage tank as desired in order to increase the activity of the bleaching solution or bleach-fixing solution, or a suitable oxidizing agent, for example, Hydrogen peroxide, bromate, persulfate and the like may be appropriately added.

In carrying out the method of the present invention, silver may be recovered from the fixing solution or the bleach-fixing solution by a known method. For example, electrolysis method (described in French Patent No. 2,299,667), precipitation method (described in Japanese Patent Application Laid-Open No. 52-73037, German Patent No. 2,331,220), ion-exchange method (described in Japanese Patent Application Laid-Open No. 51-17114) And the metal substitution method (described in British Patent 1,353,805) can be effectively used.

It is particularly preferable to recover silver in-line from the tank liquid, because the suitability for rapid processing is further improved. However, silver may be recovered from the overflow waste liquid and reused.

When the replenishing amount of the fixing solution and the bleach-fixing solution according to the present invention is 800 ml or less per 1 m ^{2 of the} light-sensitive material, the effects of the object of the present invention are more favorably exhibited. Especially the light-sensitive material 1m ² per 20
Good results are obtained with ml to 650 ml, especially 30 ml to 400 ml.

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

Good results are obtained especially at 0.3 g / l to 5 g / l, especially at 0.5 g / l to 3 g / l, most preferably at 0.8 g / l to 2 g / l.

When a compound represented by the following general formula (FA) or a compound of the following compound group (FB) is added to the fixing solution or the bleach-fixing solution according to the present invention, the effect of the object of the present invention can be improved. In addition to the effect of using a fixing solution or a bleach-fixing solution, another effect that sludge generated when a small amount of photographic material is processed over a long period of time is added. Can be

[Wherein, 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.] Specific examples represented by the general formula [FA] Typical exemplified compounds are shown below.

These compounds represented by the general formula (FA) are described in U.S. Pat.
It can be synthesized by a general method as described in US Pat. No. 335,161 and US Pat. No. 3,260,718.

Compound group [FB] FB-1 Thiourea FB-2 Ammonium iodide FB-3 Potassium iodide FB-4 Ammonium thiocyanate FB-5 Potassium thiocyanate FB-6 Sodium thiocyanate FB-7 Thiocyanocatechol The compound represented by the formula (FA) and the compound of the compound group (FB) may be used alone,
Also, two or more kinds may be used in combination. For example, thiourea and ammonium thiocyanate and ammonium iodide, thiourea and ammonium thiocyanate, (FA-12) and thiourea, (FA-12) and ammonium thiocyanate, (FA-1
2) and ammonium iodide, (FA-12) and (FA-32), (F
A-12) and (FA-38) are preferred examples. Of these, the most preferred is (FB-1),
(FB-4).

The amount of the compound represented by the general formula [FA] and the compound of the compound group [FB] is 0.1 g to 30 g per treatment solution.
Good results are obtained in the 0 g range. Especially, the range of 0.2 to 200 g is preferable, and the range of 0.5 to 150 g is particularly preferable.

In the fixer and the bleach-fixer according to the present invention, a sulfurous acid adduct is preferably used from the viewpoint of the effects of the present invention.

Examples of the compound that forms a stable sulfite adduct with the sulfite ion include a compound having an aldehyde group, a compound containing a cyclic hemiacetal, and α-
A compound having a dicarbonyl group, a compound having a nitrile group and the like can be mentioned, and preferably, a compound represented by the general formula (AI)
Compounds represented by (A-II) to (A-II) are particularly preferably used.

Preferred specific examples other than the compounds represented by formulas (AI) to (A-II) are shown below.

A ₂ , A ₃ , A ₄ and A ₅ represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a formyl group, an acyl group or an alkenyl group.
Examples of the alkyl group having 1 to 6 carbon atoms include straight-chain or branched ones, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, n-barrel and iso-barrel. And a hexane group, an isohexane group and the like, and may be substituted. Specifically, a formyl group (for example, each group such as formylmethyl and 2-formylethyl) and an amino group (for example, aminomethyl and aminoethyl) ), A hydroxyl group (for example, hydroxymethyl, 2-hydroxyethyl, 2-hydroxypropyl, etc.), an alkoxy group (for example, methoxy, ethoxy, etc.), a halogen atom (for example, chloromethyl, trichloromethyl). And each group such as dibromomethyl).

Examples of the alkenyl group include substituted and unsubstituted groups, examples of the unsubstituted group include vinyl, 2-propenyl, and the like. Examples of the substituted group include 1,2-dichloro-2.
-Carboxyvinyl, 2-phenylvinyl and the like.

Hereinafter, specific examples of the compound that forms a stable sulfite adduct with the sulfite ion will be described, but the present invention is not limited thereto.

(Exemplary compound) AO-11 Sodium formaldehyde sodium bisulfite AO-12 Sodium acetaldehyde bisulfite AO-13 Sodium propionaldehyde bisulfite AO-14 Sodium butylaldehyde bisulfite AO-21 Succinic aldehyde sodium bisulfite AO-22 Glutaraldehyde bisulfite sodium bisulfite AO- 23 β-Methylglutaraldehyde bisulfite sodium bisulfite AO-24 Maleic acid dialdehyde bisulfite sodium sulfite
It is preferably used in the range of 1 g to 80 g, more preferably 0.5 g.
g to 40 g.

The processing time of the bleaching solution and the processing solution having a fixing ability (fixing solution or bleach-fixing solution) according to the present invention is preferably 3 minutes and 45 seconds or less in total, and more preferably 20 seconds or less.
The effect of the object of the present invention is excellent when the time is 3 minutes and 20 seconds or less, particularly preferably in the range of 40 seconds to 3 minutes, and particularly preferably in the range of 60 seconds to 2 minutes and 40 seconds.

The bleaching time can be arbitrarily selected within the range of the above total time, but is preferably 1 minute and 30 seconds or less, particularly preferably 10 seconds to 70 seconds, particularly preferably 20 seconds to
55 seconds is preferred. The processing time of the processing solution having the fixing ability is as follows.
Although it can be arbitrarily selected, it is preferably 3 minutes and 10 seconds or less, particularly preferably 10 seconds to 2 seconds, in view of the effect of the object of the present invention.
Minutes 40 seconds, particularly preferably 20 seconds to 2 minutes.
The range is 10 minutes.

Further, in order to prevent bleaching fog, the crossover time between the color developing solution tank and the bleaching solution tank is preferably within 10 seconds, particularly preferably within 7 seconds, in a preferred embodiment of the present invention. .

In the processing method of the present invention, it is preferable to apply forced stirring to the bleaching solution, the fixing solution and the bleach-fixing solution. The reason for this is not only that the effects of the object of the present invention can be achieved more favorably, but also from the viewpoint of rapid processing suitability.

Here, the forced liquid stirring means that the liquid is not normally diffused and moved, but is forcibly stirred by adding a stirring means.

 Forcible stirring means include the following methods.

1.High-pressure spraying or spray stirring 2.Air bubbling 3.Ultrasonic oscillation 4.Vibration High-pressure spraying means spraying with a discharge pressure of 0.1kg / cm ² or more It refers to a method of performing processing by spraying a photosensitive material processing solution with direct treatment liquid from the nozzle, blowing the stirring method, direct treatment of the treatment liquid by applying discharge pressure 0.1 kg / cm ² or more pressure from the nozzle A method in which processing is performed by spraying a photosensitive material in a liquid, and a pressure pump or a liquid sending pump is generally used as a pressure source. Pressure pumps include plant jar pumps, gear pumps, magnet pumps, and cascade pumps.
-LPM type, 10-BFM type, 20-BFM type, 25-BFM type and the like are known as examples.

In addition, as a liquid sending pump, for example, MD-30 manufactured by Iwaki Co., Ltd.
Type, MO-56 type, MDH-25 type and MDK-32 type.

On the other hand, nozzles and spray nozzles have straight-line type, fan type,
There are a circular type, a full type, a ring type, etc., which have a strong impact force and are more effective as the photosensitive material to be processed is subjected to a slight vibration. The impact of the spray is mainly determined by the flow rate (l / min) s spray pressure (Kg / cm ² ). Therefore, there is a need for a pressurizing device capable of adjusting the pressure in proportion to the number of spray nozzles so as to sufficiently exert the effect. The most preferred pressure is 0.
If it is less than ³ to 10 kg / cm ² , no effect will be obtained, and if it is too large, the photosensitive material may be damaged or damaged.

Next, with the air bubbling treatment method, a sparger is installed at the bottom of the lower transport roller of the processing liquid tank, air or an inert gas is sent to the sparger, and the photosensitive material is vibrated by bubbles discharged from the mouth. And a method in which a processing liquid is brought into contact with the effect liquid on the front, back and side surfaces of the photosensitive material.

Suitable materials for the sparger are corrosion-resistant materials such as hard PVC, polyethylene-coated stainless steel, sintered metal, etc., and the diameter of the perforation is such that the discharged air bubbles are from 2 mm to 30 mm. If the distance is reduced from 5 mm to 15 mm, an even better effect can be obtained. As a method of sending air, an air compressor, for example, Hitachi, Ltd. Bebicon (0.4KW, BU7TL), an air pump,
For example, an air pump (Ap220 type) manufactured by Iwaki Co., Ltd. may be mentioned. The amount of air is measured per rack of the automatic processor.
From 2 l / min to 30 l / min is required, and from 5 l / min to 20 l / min, more favorable results are obtained. The amount of air or inert gas must be adjusted according to the size of the processing solution tank and the amount of photosensitive material, but the air or inert gas must be adjusted so that the vibration width of the photosensitive material due to air bubbles is from 0.2 mm to 20 mm. It is preferred to send the quantity.

Next, the ultrasonic oscillation processing method is a method in which an ultrasonic oscillator is installed in the space of the bottom or side wall in the processing solution tank of the automatic developing machine, and the photosensitive material is irradiated with ultrasonic waves to increase the development promotion efficiency. . As the ultrasonic oscillator, for example, a magnetostrictive nickel vibrator (horn type) or a magnetostrictive barium titanate vibrator (holder type) manufactured by Ultrasonic Industrial Co., Ltd. is used.

The oscillator frequency of the ultrasonic oscillator is 5-1000KHz
Of these, those having a frequency of 10 to 50 KHz are particularly preferred in view of the effects of the present invention and damage to the equipment of the automatic developing machine. As the method of irradiating the photosensitive material with the ultrasonic wave, the photosensitive material may be irradiated directly or indirectly by providing a reflection plate. However, since the ultrasonic wave is attenuated in proportion to the irradiation distance, the direct irradiation may be performed. It is more preferable to do so. The irradiation time is preferably at least one second. When the irradiation is partially performed, any of an initial stage, a middle stage, and a late stage of the treatment process may be used.

Further, the vibration treatment method is a method in which the photosensitive material is vibrated effectively between the upper roller and the lower roller in the processing solution tank of the automatic developing machine to effectively immerse the photosensitive material. As the vibrator of the vibration source, for example, V
-2B and V-4B types are generally used. The vibrator is installed in such a manner that the vibrator is fixed on the upper part of the immersion processing tank of the automatic developing machine, and the vibrator is applied from the back side of the photosensitive material. The frequency of the vibrator is preferably 100 to 10,000 times / min. The most preferred range is 500-6000 cycles / min.
The amplitude of the light-sensitive material to be processed is 0.2 mm to 30 mm, preferably 1
mm to 20 mm. 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 oscillators varies depending on the size of the automatic developing machine. However, when the processing tank is composed of multiple tanks, a preferable effect can be obtained by installing one or more at least one processing tank in each processing tank.

In the present invention, the processing time of the silver halide color photographic light-sensitive material with the color developing solution is preferably 210 seconds or less and 10 seconds or more.In the processing method of the silver halide color photographic light-sensitive material of the present invention, the color developing solution is A color developing solution containing an aromatic primary amine-based color developing solution main agent preferably in an amount of 5.0 × 10 ^-3 mol or more per processing solution. More preferably 1.0 × 10
^-2 mol or more, more preferably 1.2 × 10 ^-2 to 2 × 10 ^-1
Color developing solutions containing molar developing agents are preferred.

Hereinafter, the color developing agent of the color developing solution that can be preferably used in the present invention will be described.

The aromatic primary amine-based color developing agents used in the preferred color developing solution include known ones widely used in various color photographic processes.
These developers include aminophenol-based and p-phenylenediamine-based derivatives. These compounds are generally used in the form of a salt, for example in the form of a hydrochloride or a sulfate, for stability in the free state. Examples of the aminophenol-based developer include o-aminephenol, p-aminophenol, 5-amino-2-oxy-toluene, and 2-aminophenol.
Amino-3-oxy-toluene, 2-oxy-3-amino-1,4-dimethyl-benzene and the like.

In the present invention, an aromatic primary amine color developing agent that is particularly useful in the present invention because the desired effect is more favorably exhibited and the crystal deposition property on the inner wall of the color developing tank of the automatic developing machine is improved. It is an aromatic primary amine color developer having an amino group having at least one water-soluble group, and is particularly preferably a compound represented by the following general formula [E].

In the formula, R ¹ represents a hydrogen atom, a halogen atom or an alkyl group, and the alkyl group is a straight-chain or branched carbon atom having 1 to 5 carbon atoms.
And may have a substituent.

R ² and R ³ represent a hydrogen atom or an alkyl group or an aryl group, and these groups may have a substituent. And at least one of R ² and R ³ are a hydroxyl group, a carboxylic acid group, a sulfonic acid group, an amino group, a water-soluble group such as a sulfonamido group is an alkyl group or (CH _{2 ⁴} O _P R ₄ was replaced. The The alkyl group may further have a substituent.

R ⁴ represents a hydrogen atom or an alkyl group, and the alkyl group represents a linear or branched alkyl group having 1 to 5 carbon atoms, and p and q each represent an integer of 1 to 5.

Next, a compound represented by the above general formula (E) will be mentioned.
It is not limited to these.

(Exemplary compound) These p-phenylenediamine derivatives represented by the general formula [E] can be used as salts of organic acids and inorganic acids, for example, hydrochloride, sulfate, phosphate, p-toluenesulfonate, sulfite, oxalic acid Salts, benzenedisulfonic acid salts and the like can be used.

In the present invention, among the P-phenylenediamine derivatives represented by the general formula [E], E-1 and E-2 are most preferably used, and the effect of the present invention is remarkably exhibited.

As a preservative used in the color developing solution used in the present invention, there is a sulfite, and as the sulfite, there are sodium sulfite, sodium bisulfite, potassium sulfite, potassium bisulfite, etc., and the silver halide is substantially a silver chloride emulsion. In this case, the sulfite is 1.0 × 10 ⁻² mol / l or less, preferably 5.0 × 10 ⁻³ mol / l or less, particularly preferably 0. When the silver halide is a silver iodobromide emulsion, the sulfite is
It is preferably used in the range of 0.1 to 40 g / l, more preferably in the range of 0.5 to 10 g / l.

Further, as preservatives other than sulfites, hydroxylamine and JP-A-63-146043, JP-A-63-146042, 63-146
146041, 63-146040, 63-135938, 63-11
No. 8748, hydroxylamine derivative and JP-A-64-
No. 62639, hydroxamic acids, hydrazines, hydrazides, phenols, α-hydroxyketones, α
-Aminoketones, sugars, monoamines, diamines,
Quaternary ammonium salts, nitroxy radicals, alcohols, oximes, diamide compounds, condensed amines, and the like are preferably used as organic preservatives.

In particular, when the silver halide is a high concentration of silver chloride, organic preservatives other than hydroxylamine, particularly, alkyl-substituted hydroxylamine derivatives and hydrazines are preferably used.

Further, as the development inhibitor preferably used in the color developing solution, in addition to halides such as sodium chloride, potassium chloride, sodium bromide, potassium bromide, sodium iodide and potassium iodide, there are also organic inhibitors. The amount of addition is preferably in the range of 0.005 to 30 g / l, more preferably in the range of 0.01 to 20 g / l.

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

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

Among the above-mentioned organic inhibitors, the following general formula [R
-I], [R-II] and [R-III].

The compound represented by the following general formula [RI] is more preferably a compound represented by the general formula [R-IV] or [RV], and most preferably the compound represented by the general formula [R-VI] to
It is a compound represented by [R-XI].

On the other hand, the compound represented by the following general formula [R-II] is most preferably a general formula [R-XII] or [R-XII].
I].

In the formula, X and X ₁ are a halogen atom, a mercapto group, an oxycarbonyl group, an alkyl group, an aryl group, an amino group, a hydroxyl group, a nitro group, a carboxyl group, a smho group, X ₂ is a hydrogen atom, an alkyl group, an aryl group or 2 shows a double bond for forming a ring. Z represents a group consisting of a carbon atom, a nitrogen atom, and a sulfur atom necessary for forming a ring, and n and m each represent 0, 1 or 2. When n and m are 2, each X and X ₁ may be the same or different.

In the formula, Y, Y ₁ , Y ₂ and Y ₃ represent a hydrogen atom, a halogen atom, an alkyl group, an amino group, a hydroxyl group, a nitro group, a carboxyl group, an oxycarbonyl group, a sulfo group, and a sulfonyl group.

In the formula, T is a nitrogen atom or a phosphorus atom, X ₂ and X ₃ are a hydrogen atom,
An alkyl group, an aryl group, a halogen atom, Y ₄ and Y ₅ represent an alkyl group or an aryl group, and Y ₄ and Y ₅ may be closed to form a hetero ring.

Compounds having 2 to 5 carbon atoms substituted by nitrogen atoms and derivatives thereof Compounds having 1 to 5 carbon atoms substituted with 2 to 4 nitrogen atoms and derivatives thereof In each of the formulas [R-IV] to [R-XIII], R, R ₁ , R ₂ , Y ₁ ,
Y ₂ has the same meaning as Y, Y ₁ , Y ₂ and Y _{3 in} the description of [R-II]. m and n have the same meaning as in the general formula and [RI].

By using the organic inhibitor in combination with the inorganic inhibitor of 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, and more specifically, the above-mentioned Japanese Patent Application No. 61-12781.
(Z-I) to (Z-) on pages 101 to 113 of the specification
3), (Z-6), (Z-8), (Z-13), (Z-1
5) to (Z-17), (Z-19), (Z-22) to (Z-2)
5), (Z-29), (Z-31) to (Z-38), (Z-4
0), (Z-41), (Z-43) to (Z-64) and (Z-6)
6) to (Z-73).

In the color developer used in the present invention, various components which are usually added, for example, sodium hydroxide,
An alkali agent of sodium carbonate sugar, an alkali metal thiocyanate, an alkali metal halide, benzyl alcohol, a water softening agent, a thickening agent, a development accelerator and the like can be optionally contained.

Other additives to be added to the color developing solution include a stain inhibitor, a sludge inhibitor, a preservative, a multilayer effect promoter, a chelating agent, and the like.

The color developing solution of the present invention is preferably used at pH 9 or more, particularly at pH 9 to 13.

Further, the processing temperature of the color developing solution is preferably 30 ° C. or higher, and particularly preferably in the range of 33 ° C. to 60 ° C., in order to more effectively achieve the effects of the present invention.

Next, the stabilizer used in the present invention will be described.
The stabilizing solution used in the present invention can be applied to a stabilizing solution used in a stabilizing process which is a final processing step of a silver halide color photographic light-sensitive material. The present invention is also applicable to a case where a silver halide color photographic light-sensitive material is processed with a processing solution having a fixing ability, for example, a fixing solution or a bleach-fixing solution, and subsequently subjected to a stabilization process without substantially washing with water. You can also. The silver halide color photographic light-sensitive material to be processed is not particularly limited, such as a negative film, photographic paper, color copy, etc., and can be processed using the stabilizer of the present invention.

The replenishment amount of the stabilizer of the present invention is preferably 1 to 80 times the carry-in amount from the previous bath per unit area of the color photographic material to be processed. Or fixer solution) in the last tank of the stabilizing solution tank.
1/100 or less, 1/100 to 1/10 in terms of low pollution and liquid storage
It is preferable to configure the treatment tank of the stabilization tank so as to have a ratio of 0000, preferably 1/200 to 1 / 50,000.

The stabilization tank may be composed of a plurality of tanks, and it is preferable for the present invention that the plurality of tanks be two tanks or more and six tanks or less.

In the present invention, in the case of two or more tanks, it is particularly preferable to use a counter current method (a method of supplying to a post-bath and overflowing from a pre-bath) from the viewpoint of the effects of the present invention, particularly, low pollution and improvement of image preservation.

The carry-in amount varies depending on the type of photosensitive material, the transport speed of the automatic developing machine, the transport method, the squeeze method on the photosensitive material surface, etc., but in the case of a color photosensitive material, the carry-in amount is usually 50 ml / m ^2.
~ 150 mL / m ^2, replenishment rate effect is more pronounced in the present invention for this amount carried is in the range of ^{50ml / m 2 ~4.0l / m 2} , the effect is particularly noticeable replenishment rate 100 ml / m ^{2 ~1500ml} / m ²
In the range.

The treatment temperature of the treatment with the stabilizing solution is 15 to 60 ° C, preferably
Good range is 20-45 ° C.

Further, in the stabilizer of the present invention, the following general formula [CH-I]
It is preferable to include a chelating agent represented by the formula [CH-III].

(Wherein, E is an alkylene group, a cycloalkylene group, a phenylene _{group, -R 5 '-O-R 5} ' -, - R 5 '-O-R 5' -0
-R ₅ '-, or _{-R 5' -Z-R 5 '} - represent.

Represents

R ₁ ′ to R ₆ ′ each represent an alkylene group. A _{1 to} A ₃
Represents -COOM or -PO ₃ M _2, respectively, A ₄ and A ₅
Represent each a hydrogen atom, a hydroxyl group, a -COOM or -PO ₃ M _2. M represents a hydrogen atom or an alkali metal atom. ) (Wherein R ₇ ′ is an alkyl group, an aryl group or a nitrogen-containing 6
Represents a membered ring group. M represents a hydrogen atom or an alkali metal atom. ) (Wherein R ₈ ′, R ₉ ′ and R ₁₀ ′ are each a hydrogen atom,
Hydroxyl, -COOM, and -PO ₃ M ₂ or an alkyl group represents, B
₁ , B ₂ and B ₃ are each a hydrogen atom, a hydroxyl group, Represents J represents a hydrogen atom, an alkyl group, a -C ₂ H ₄ OH or -PO ₃ M _2. M represents a hydrogen atom or an alkali metal atom, and n and m each represent 0 or 1.

The general formulas [CH-I], [CH-II] and [CH-III]
The following shows a part of specific examples of the chelating agent represented by. The chelating agent used in the present invention is not limited to the following specific examples.

(Example chelating agent)

The chelating agent preferably used in the above-mentioned stabilizer is preferably used in an amount of 0.01 to 100 g, more preferably 0.05 to 50 g, and particularly preferably 0.1 to 20 g, per one of the stabilizer of the present invention.

Further, the pH value of the stabilizer is preferably in the range of pH 4.0 to 9.0 for the purpose of improving image storability, more preferably.
It is in the range of 5.5 to 9.0, particularly preferably in the range of pH 6.0 to 8.5.

As the pH adjuster that can be contained in the stabilizing solution, any commonly known alkali agent or acid agent can be used.

Stabilizers include organic acid salts (citric acid, acetic acid, succinic acid,
Oxalic acid, benzoic acid, etc.), pH adjusters (phosphate, borate, hydrochloric acid, sulfate, etc.), surfactants, preservatives, Bi, Mg,
Metal salts such as Zn, Ni, Al, Sn, Ti, and Zr can be added. These compounds should be used in any combination in amounts that are necessary to maintain the pH of the stabilizing bath, and that do not adversely affect the stability during storage of color photographic images and the occurrence of precipitation. I can't wait. It is also preferable that the Ca and Mg ions in the stabilizing solution be 5 ppm or less from the viewpoint of achieving the above effects.

Antifungal agents preferably used in the stabilizer used in the present invention include hydroxybenzoic acid ester compounds, phenolic compounds, thiazole compounds, pyridine compounds, guanidine compounds, carbamate compounds, morpholine compounds, and quaternary phosphonium compounds. Compounds, ammonium compounds, urea compounds, isoxazole compounds, propanolamine compounds, sulfamide compounds, amino acid compounds and benzotriazole compounds.

Furthermore, a phenol compound, a thiazole compound and a benztriazole compound are particularly preferable from the viewpoint of liquid preservation.

Specific examples include 1,2-benzisothiazolin 3-one, 2-methyl-4-isothiazolin 3-one, 2-octyl-4-isothiazolin 3-one, 5-chloro-2-
Methyl-4-isothiazolin-3-one, 0-phenylphenol sodium, benzotriazole and the like can be mentioned. The amount of these fungicides to be added to the stabilizer is 0.
It is preferably in the range of 001 g to 20 g, particularly preferably 0.005 g to 1 g.
It is in the range of 0g.

Further, the stabilizing solution of the present invention contains formalin, hexamethylenetetramine, triazine-based compound, N-methylol compound (dimethylolurea, trimethylolurea, dimethylolguanidine, N-hydroxymethylhydroxyethylamine, Trimethylol melamine, etc.), aliatic aldehyde, etc. can be used in combination, but it is preferable to make formalin substantially zero from the viewpoint of pollution, and in a preferred embodiment from the viewpoint of liquid preservation. is there.

The stabilizer used in the present invention more preferably contains a sulfite ion-releasing compound and at least one of the compounds represented by the following general formulas (SA) and (SB), and has no adverse effect on photographic performance. And the storage stability of the solution is further improved.

In the formula, A ₁ , A ₂ , A ₃ and A ₄ each represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a formyl group, an acyl group or an alkenyl group. M represents an alkali metal atom (Na, K, Li, etc.). n represents an integer of 1 to 5.

Examples of the alkyl group having 1 to 6 carbon atoms include straight-chain or branched ones, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, n-barrel, isovaler, and hexane. , Isohexane group and the like, and may be substituted. Specific examples include a formyl group (for example, each group such as formylmethyl and 2-formylethyl) and an amino group (for example, each group such as aminomethyl and aminoethyl). ), A hydroxyl group (for example, hydroxymethyl, 2-hydroxyethyl, 2-hydroxypropyl, etc.), an alkoxy group (for example, methoxy, ethoxy, etc.), a halogen atom (for example, chloromethyl, trichloromethyl, dibromomethyl, etc.) And the like).

Examples of the alkenyl group include substituted and unsubstituted groups, examples of the unsubstituted group include vinyl, 2-propenyl, and the like. Examples of the substituted group include 1,2-dichloro-2.
-Carboxyvinyl, 2-phenylvinyl and the like.

Hereinafter, specific examples of the compounds represented by the general formulas (SA) and (SB) will be described, but the present invention is not limited thereto.

(Exemplary compound)

SA-1 Sodium formaldehyde sodium bisulfite SA-2 Sodium acetaldehyde bisulfite SA-3 Propionaldehyde sodium bisulfite SA-4 Sodium butyraldehyde bisulfite SB-1 Sodium succinaldehyde bisulfite SB-2 Glutaraldehyde bis sodium bisulfite SB- 3 Sodium β-methylglutaraldehyde bisulfite SB-4 Sodium maleate dialdehyde bisbisulfite The compounds represented by the above general formulas (SA) and (SB) may be used alone or in combination. The amount of the stabilizer is preferably 0.1 to 50 g, more preferably 0.1 to 20 g, per 1 stabilizing solution of the present invention.

The sulfite ion releasing compound used in the present invention may be any substance such as an organic substance and an inorganic substance as long as it releases sulfite ions, but is preferably an inorganic salt, and a preferred specific compound is SC-1 sodium sulfite SC -2 Potassium sulfite SC-3 Ammonium sulfite SC-4 Ammonium bisulfite SC-5 Potassium bisulfite SC-6 Sodium bisulfite SC-7 Sodium metabisulfite SC-8 Potassium metabisulfite SC-9 Ammonium metabisulfite SC- 10 hydrosulfite.

The addition amount of the sulfite ion-releasing compound to the treatment solution capable of simultaneously performing the washing alternative stabilizing solution, the stabilizing solution and the washing alternative stabilization and stabilization treatment is preferably 0.01 to 0.1 mol / l, more preferably 0.02 to 0.1 mol / l. l.

Further, the stabilizer used in the present invention has a general formula [I],
It preferably contains the surfactant represented by [III], triethanolamine, and polyvinylpyrrolidone.

General formula [I] R ₁ -OR ₂ -O _m X ₁ (wherein, R ₁ represents a monovalent organic group, R ₂ represents an ethylene group or a propylene group, and m represents an integer of 4 to 50) .X ₁ represents a hydrogen atom or a -SO ₃ M or -PO ₃ M _2. wherein M represents a hydrogen atom, an alkali metal atom or -NH _4.

Specific exemplary compounds include: These compounds represented by the above general formula [I] can be used in the stabilizer of the present invention in an amount of 0.1 to 40 g, preferably 0.3 to 20 g per one.

As the polyvinylpyrrolidone used in the present invention, those having an average molecular weight of 1,000 to 70,000 are preferable, and representative examples thereof include the following.

(Exemplary compound)

[P-1] Poly-N-vinyl-2-pyrrolidone (* Note I) [P-2] Poly-N- (2-acryloyloxy) ethyl-1-pyrrolidone [P-3] Poly-N-glycidyl- 2-pyrrolidone [P-4] poly-N-allyl-2-pyrrolidone [P-5] poly-N, N-dimethyl-N- [3 (1-pyrrolidonyl) -2-hydroxy] propyl-amine-
N'-acryloylimin [P-6] copoly-N-vinyl-2-pyrrolidone / N-
Acryloylmorpholine (molar ratio 42:58) [P-7] Copoly-N-vinyl-2-pyrrolidone / N-
Acryloylpiperidine (35:65 molar ratio) [P-8] Poly-N-vinyl-2-pyrrolidone / N-methacryloyl-2-methylimidazole (55: 4 molar ratio)
5) [P-9] Copoly-N- (2-acryloyloxy)
-Ethyl-2-pyrrolidone / acrylic acid diethylamide (molar ratio 60:40) [P-10] copoly-N- (2-methacryloyloxy)
Ethyl-2-pyrrolidone / sodium acrylate (molar ratio 75:25) [P-11] copoly-N- (3-acryloyloxy) propyl-2-pyrrolidone / methyl methacrylate (molar ratio)
65:35) [P-12] copoly-N, N-dimethyl-N- [3 (1-pyrrolidonyl) -2-hydroxy] -propylamine-
N'-acryloylimin / ethyl acrylate (molar ratio
70:30) [P-13] Copoly-N-vinyl-2-pyrrolidone / vinyl acetate (molar ratio 70:30) [P-14] Copoly-N-vinyl-2-pyrrolidone / methyl acrylate (molar ratio 70 : 30) [P-15] copoly-N-vinyl-2-pyrrolidone / styrene (molar ratio 80:20) [P-16] copoly-N-vinyl-2-pyrrolidone / acrylamide / N-vinyl-2 -Methylimidazole (molar ratio 50:30:20) [P-17] copoly-N-vinyl-2-pyrrolidone / N-
(1,1-dimethyl-3-oxo) -butyl-acrylamide (molar ratio 70:30) [P-18] copoly-N-allyl-2-pyrrolidone / vinyl acetate (molar ratio 64:36) [P-19 ] Copoly-N-vinyl-2-pyrrolidone / 4-vinylpyridine (molar ratio 60:40) [P-20] Copoly-N-vinyl-2-pyrrolidone / ethyl acrylate / ethyl acrylate / monoethanolamine acrylate Acid (molar ratio 50: 45: 5) [P-21] copoly-N-vinyl-2-pyrrolidone / piperidinomaleamic acid piperidic acid (molar ratio 53:47) [P-22] Copoly-N-vinylpyrrolidone / 4-Vinylpyridino-N-methyl iodide (Molar ratio 42:58) [P-23] Copoly-N-vinylpyrrolidone / maleic acid thiourea half-ammonium salt (Molar ratio 60:40) * Note (1) Exemplary compound [P-1] is General A General Aniline And Fi
lm Corp.) from PVP K-15, PVP K-17, PVP K-30, PVP K
-60, PVP K-90 and BASF Aktiengesellschaft, Kollidon 12,
Kollidone 17, Kollidon 25, Kollidon 30, Kollidon 90, Luviscol K-17, Luviscol K-30, Luviscol K-90
It is commercially available under the trade name.

As described above, the polymer or copolymer of the present invention can be easily obtained because a part of the polymer or copolymer is commercially available, or issued by John Wilery and Sons, Inc. (1961). Year) Preparat Method of Polymer Chemistry by WR Sorenson, TWCampbell
ive Methods of Polymer Chemistry).

The polymer or copolymer of the present invention may be used alone or in combination of two or more, and the amount used is in the range of 0.01 g to 100 g per image stabilizer, preferably
It is in the range of 0.05 g to 10 g. Incidentally, the polymer or copolymer of the present invention may be used in a mode in which the polymer or copolymer may be added to the stabilizer or added to the replenisher to replenish the stabilizer.
You may use these both together.

(Wherein R ₉ is a hydrogen atom, a hydroxy group, a lower alkyl group, an alkoxy group, Represents R ₁₀ , R ₁₁ and R ₁₂ each represent a lower alkyl group (preferably an alkyl group having 1 to 3 carbon atoms, such as methyl, ethyl, propyl, etc.);
_10, R ₁₁ and R ₁₂ may respectively be the same or different.

l _{1 to} l ₃ each represent 0 or an integer of 1 to 4, p,
Each q ₁ and q ₂ is an integer of 1 to 15. Hereinafter, specific examples of the compound represented by the general formula [III] will be shown.

(Water-soluble organic siloxane compound) When the amount of the water-soluble organic siloxane-based compound to be added is in the range of 0.01 to 20 g per 1 stabilizing solution, a good effect is exhibited.

If the amount is 0.01 g or less, the surface of the photosensitive material is conspicuous, and if the amount is 20 g or more, a large amount of the organic siloxane compound adheres to the surface of the material and becomes contaminant.

The water-soluble organic siloxane compound of the present invention includes, for example,
JP-A-47-18333, JP-B-55-51172, JP-B-51-37
No. 538, JP-A-49-62128 and U.S. Pat.
It means a general water-soluble organic siloxane-based compound as described in, for example, JP-A-970.

These water-soluble organic siloxane compounds can be generally obtained from UCC (Union Carbide), Shin-Etsu Chemical Co., Ltd., or the like.

The light-sensitive material according to the present invention is prepared by an internal developing method in which a coupler is contained in the light-sensitive material (US Pat. No. 2,376,679;
In addition to the external developing method in which a coupler is contained in a developer (see U.S. Pat. Nos. 2,252,718 and 2,592),
Nos. 2,243 and 2,590,970).
Any coupler generally known in the art can be used as the coupler. For example, as the cyan coupler, those other than the present invention may be used in combination, and the cyan coupler used in combination is one having a naphthol or phenol structure as a base and forming an indoaniline dye by coupling, as a magenta coupler. Is a compound having a 5-pyrazolone ring having an active methylene group as a skeleton structure and a pyrazoleazole compound, and a yellow coupler having a benzoylacetanilide, pivalyl acetanilide, or acylacetanilide structure having an active methylene ring is used as a coupling position. And those having no substituent can be used. As described above, as the coupler, any of a so-called 2-equivalent coupler and a 4-equivalent coupler can be applied.

When the color photographic light-sensitive material is a negative light-sensitive material (for example, a color negative film), preferred cyan couplers include those represented by the following general formulas [CA], [CB], and [CC]. .

In the formula, R ₁ represents an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group or a heterocyclic group, and Y is In a group represented by (wherein R ₂ represents an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group or a heterocyclic group, R ₃ is .R ₂ represents a group represented by a hydrogen atom or R ₂
And R ₃ may be the same or different and are linked together to form 5
A 6-membered heterocyclic ring may be formed. ) And Z represent a hydrogen atom or a group which can be eliminated by a coupling reaction with an oxidized form of an aromatic primary amine color developing agent.

R ₁₁ is -CONR ₁₄ R ₁₅ , -NHCOR ₁₄ , -NHCOOR ₁₆ , -NHSO ₂
R ₁₆ , -NHCONR ₁₄ R ₁₅ or -NHSO ₂ NR ₁₄ R ₁₅ , R ₁₂ are monovalent groups, R ₁₃ is a substituent, X is a hydrogen atom or an aromatic primary amine. L is 0 or 1, m is 0 to 3, R ₁₄ and R ₁₅ are a hydrogen atom, an aromatic group, an aliphatic group or a heterocyclic group, R ₁₆ is an aromatic group, an aliphatic group or a heterocyclic group And when m is 2 or 3, each R ₁₃ may be the same or different, and may combine with each other to form a ring, and R ₁₄ and R ₁₅ , R ₁₂ and R ₁₃ , and R ₁₂ X may combine to form a ring. However, when 1 is 0, m is 0 and R ₁₁ is -C
ONHR ₁₇ , where R ₁₇ represents an aromatic group.

First, the general formulas [CA] and [CB] will be described. In the formula, Y is Is a group represented by Here, R ₁ and R ₂ are each an alkyl group, preferably an alkyl group having 1 to 20 carbon atoms (for example, each group of methyl, ethyl, t-butyl, dodecyl, etc.), an alkenyl group, preferably an alkenyl having 2 to 20 carbon atoms. Group (e.g., allyl group, heptadecenyl group), cycloalkyl group, preferably 5- to 7-membered ring (e.g., cyclohexyl), aryl group (e.g., phenyl group, tolyl group, naphthyl group, etc.), heterocyclic group, preferably Represents a 5- to 6-membered ring group containing 1 to 4 nitrogen atoms, oxygen atoms or sulfur atoms (for example, a furyl group, a thienyl group, a benzothiazolyl group, etc.). R ₃ represents a hydrogen atom or a group represented by R ₂ . R ₂ and
R ₃ may combine with each other to form a 5- to 6-membered heterocyclic ring. Any substituent can be introduced into R ₁ and R ₂ , for example, an alkyl group having 1 to 10 carbon atoms (eg, methyl, i-propyl, i-butyl, t-butyl, t-octyl, etc.) An aryl group (eg, phenyl, naphthyl, etc.), a halogen atom (fluorine, chlorine, bromine, etc.), a cyano, nitro, sulfonamide group (eg, methanesulfonamide, butanesulfonamide, p-toluenesulfonamide, etc.), a sulfamoyl group ( Methylsulfamoyl, phenylsulfamoyl, etc.), sulfonyl group (eg, methanesulfonyl, p-toluenesulfonyl, etc.), fluorosulfonyl group, carbamoyl group (eg, dimethylcarbamoyl, phenylcarbamoyl, etc.), oxycarbonyl group (eg, ethoxycarbonyl, Phenoxycarbonyl), an acyl group (for example, Chill, benzoyl, etc.), heterocyclic (e.g. pyridyl group, pyrazolyl group, etc.), alkoxy and the like, an aryloxy group, and an acyloxy group.

In the general formulas [CA] and [CB], R ₁
Represents a ballast group necessary for imparting diffusion resistance to a cyan coupler represented by the general formulas [CA] and [CB] and a cyan dye formed from the cyan coupler. It is preferably an alkyl group having 4 to 30 carbon atoms, an aryl group, an alkenyl group, a cycloalkyl group or a heterocyclic group. For example, a linear or branched alkyl group (for example, t-
Butyl, n-octyl, t-octyl, n-dodecyl, etc.) and a 5- or 6-membered heterocyclic group.

In the general formulas [CA] and [CB], Z
Represents a hydrogen atom or a group capable of leaving during a coupling reaction with an oxidized form of a color developing agent. For example, a halogen atom (eg, chlorine, bromine, fluorine, etc.), a substituted or unsubstituted alkoxy group, an aryloxy group, a heterocyclic oxy group, an acyloxy group, a carbamoyloxy group, a sulfonyloxy group, an alkylthio group, an arylthio group, a heterocyclic group Examples thereof include thio groups and sulfonamide groups.More specific examples include U.S. Pat.No. 3,741,563, JP-A-47-37425, JP-B-48-36894, JP-A-50-10135, and 50-117422. issue,
No. 50-130441, No. 51-108841, No. 50-120343, No.
No. 52-18315, No. 53-105226, No. 54-14736, No. 54-
48237, 55-32071, 55-65957, 56-1938
No. 56-12643, No. 56-27147, No. 59-146050,
Nos. 59-166696, 60-24547, 60-35731, 60
-37557 and the like.

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

In the general formula [CD], R ₄ is a substituted or unsubstituted aryl group (particularly preferably a phenyl group). When the aryl group has a substituent, examples of the substituent include SO ₂ R ₅ ,
Halogen atoms (fluorine, chlorine, bromine, etc.), - CF _3, -N
_{O 2, -CN, -COR 5,} -COOR 5, -SO 2 OR 5, And at least one substituent selected from the group consisting of:

Here, R ₅ is an alkyl group, preferably an alkyl group having 1 to 20 carbon atoms (for example, each group of methyl, ethyl, t-butyl, dodecyl and the like), an alkenyl group, preferably 2 to 20 carbon atoms.
Alkenyl group (such as allyl group and heptadecenyl group), cycloalkyl group, preferably those having a 5- to 7-membered ring (such as cyclohexyl), and aryl group (such as phenyl group,
R ₆ is a hydrogen atom or a group represented by R ₅ .

Preferred compounds of the cyan coupler of the present invention represented by the general formula [CD] are those in which R ₄ is a substituted or unsubstituted phenyl group, and cyano, nitro,
—SO ₂ R ₇ (where R ₇ is an alkyl group), a halogen atom, and trifluoromethyl.

In the general formula [CD], Z and R ₁ each represent the general formula [C
-A] and [CB]. Preferred examples of the ballast group represented by R ₁ are those represented by the following general formula [C-
E].

In the formula, J represents an oxygen atom, a sulfur atom or a sulfonyl group, K represents an integer of 0 to 4, 1 represents 0 or 1, and K represents
There is R ₉ where there are two or more in the case of more than one may be the same or different, R ₈ represents a substituted alkylene group such as a straight-chain or branched, and aryl groups having 1 to 20 carbon atoms, R ₉ is Represents a monovalent group, preferably a hydrogen atom, a halogen atom (for example, chromium or bromo), an alkyl group, preferably a linear or branched alkyl group having 1 to 20 carbon atoms (for example, methyl, t-butyl, t-pentyl) , T-octyl, dodecyl, pentadecyl, benzyl, phenethyl, etc.), aryl group (for example, phenyl group), heterocyclic group (for example, nitrogen-containing heterocyclic group), alkoxy group, preferably linear or branched carbon number 1 to 20 alkoxy groups (for example, methoxy, ethoxy,
t-butyloxy, octyloxy, decyloxy, dodecyloxy, etc.), aryloxy group (eg, phenoxy group), hydroxy group, acyloxy group, preferably alkylcarbonyloxy group, arylcarbonyloxy group (eg, acetooxy group, benzoyloxy) Group), carboxy, alkyloxycarbonyl group, preferably linear or branched alkylcarbonyl group having 1 to 20 carbon atoms, preferably phenoxycarbonyl group, alkylthio group, preferably acyl group having 1 to 20 carbon atoms, preferably carbon atom A linear or branched alkylcarbonyl group of numbers 1 to 20,
An acylamino group, preferably a linear or branched alkylcarbonamide group having 1 to 20 carbon atoms, a benzenecarbamide group, a sulfonamide group, preferably a linear or branched alkylsulfonamide group having 1 to 20 carbon atoms or benzenesulfone Amido group, carbamoyl group, preferably having 1 to 1 carbon atoms
20 represents a linear or branched alkylaminocarbonyl group or a phenylaminocarbonyl group, a sulfamoyl group, preferably a linear or branched alkylaminosulfonyl group or a phenylaminosulfonyl group having 1 to 20 carbon atoms.

Next, specific examples of the cyan coupler of the present invention represented by the general formula [CA] or [CB] are shown below, but the invention is not limited thereto.

(Exemplary compound)

Next, the general formula [CC] will be described.

Each of the groups represented by R _{12 to} R ₁₇ in the general formula [CC] includes those having a substituent.

As R ₁₆ , an aliphatic group having 1 to 30 carbon atoms, 6 to 30 carbon atoms
Aromatic group, a heterocyclic group having 1 to 30 carbon atoms is preferable, and R
_14, those as R ₁₅ is listed as preferred as a hydrogen atom and R ₁₆ are preferred.

R ₁₂ is a hydrogen atom bonded to NH directly or via NH, CO or SO ₂ , an aliphatic group having 1 to 30 carbon atoms, and 6 carbon atoms.
To 30 aromatic groups, a heterocyclic group having 1 to 30 carbon atoms, -OR ₁₈ ,
−COR _{18 -POOR 20) 2, -POR 20)} 2, -CO 2 R 20, -SO 2 R 20 or _{-SO 2 OR 20 (R 18,} R 19 and R ₂₀ are the respective
As defined for R ₁₄ , R ₁₅ and R ₁₆ , R ₁₈ and R ₁₉ may combine to form a heterocycle. )
Is preferred.

R ₁₇ is preferably an aromatic group having 6 to 30 carbon atoms,
Representative examples of the substituent of ₁₇ include a halogen atom, a hydroxy group, an amino group, a carboxyl group, a sulfonic acid group, a cyano group, an aromatic group, a heterocyclic group, a carbonamide group, a sulfonamide group, a carbamoyl group, a sulfamoyl group, Ureido group, acyl group, acyloxy group, aliphatic oxy group,
Aromatic oxy group, aliphatic thio group, aromatic thio group, aliphatic sulfonyl group, aromatic sulfonyl group, sulfamoylamino group, nitro group, imide group, aliphatic group, aliphatic oxycarbonyl group, etc. Can be. When substituted with a plurality of substituents, the plurality of substituents may be bonded to each other to form a ring, and examples thereof include a dioxymethylene group.

Representative examples of R ₁₃ include a halogen atom, a hydroxy group,
Amino group, carboxyl group, sulfonic group, cyano group,
Aromatic group, heterocyclic group, carbonamido group, sulfonamido group, carbamoyl group, sulfamoyl group, ureido group, acyl group, acyloxy group, aliphatic oxy group, aromatic oxy group, aliphatic thio group, aromatic thio group , An aliphatic sulfonyl group, an aromatic sulfonyl group, a sulfamoylamino group, a nitro group, and an imide group.
_The number of carbon atoms contained in ₁₃ is preferably from 0 to 30. When m = 2, examples of the cyclic R ₁₃ include a dioxymethylene group.

When 1 is 1, R ₁₁ is particularly preferably -CONR ₁₄ R ₁₅ ;
Is preferably 0, and R ₁₂ is directly bonded to NH—COR ₁₈ , —CO
OR ₂₀ , —SO ₂ R ₂₀ , —CONR ₁₈ R ₁₉ , and —SO ₂ NR ₁₈ R ₁₉ are particularly preferred, and more preferably —COO directly bonded to NH.
R ₂₀ , —COR ₁₈ and —SO ₂ R ₂₀ , among which —COOR ₂₀ is most preferred.

Further, those forming multimers of dimers or more via R _{11 to} R ₁₃ and X are also included in the present invention.

 Among the general formulas [CC], the case where l = 0 is preferable.

Specific examples of the coupler represented by the general formula [CC] are described in JP-A-60-237448, JP-A-61-153640, JP-A-61-145557, and JP-A-61-145557.
No. 62-85242, No. 48-15529, No. 50-117422, No. 52-
18315, 52-90932, 53-53423, 54-48237
No. 54-66129, No. 55-32071, No. 55-65957,
No. 55-105226, No. 56-1938, No. 56-12643, No. 56
-27147, 56-126632, 58-95346 and U.S. Pat. No. 3,488,193, and can be synthesized by the methods described therein.

Depending on the physical properties (eg, solubility) of the coupler, an oil-in-water emulsion dispersion method using a water-insoluble high-boiling organic solvent, an alkali dispersion method of adding as an alkaline solution, and a latex dispersion may be used depending on the physical properties (eg, solubility) of the coupler. Various methods can be used, such as a solid dispersion method in which a solid is directly added as a fine solid.

The amount of the coupler to be added is usually 1.0 per mole of silver halide.
× 10 ⁻³ mol to 1.0 mol, preferably 5.0 × 10 ⁻³ mol to 8.0
× 10 ^-1 mol.

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

(Exemplary compound)

When the color photographic light-sensitive material is a positive light-sensitive material (for example, color negative paper), preferred cyan couplers include those represented by the following general formula [C-1].

[Wherein, R ₁ represents a ballast group, and R ₂ represents an alkyl group having 2 or more carbon atoms. Z ₁ represents a hydrogen atom or an atom or a group which can be eliminated by reaction with an oxidized form of a color developing agent. In the cyan coupler represented by the general formula [C-1], the alkyl group represented by R ₂ may be linear or branched, and includes those having a substituent.

R ₂ is preferably an alkyl group having 2 to 6 carbon atoms.

Ballast group represented by R ₁ is an organic group having at the size and shape to be given to the coupler molecule sufficient bulky to Prevent diffuse couplers from layers coupler is applied to substantially the other layer It is.

Preferred as the ballast group are those represented by the following general formula.

R _B1 represents an alkyl group having 1 to 12 carbon atoms, and Ar is
Represents an aryl group such as a phenyl group, and the aryl group includes those having a substituent.

Next, specific examples of the coupler represented by the general formula [C-1] are shown, but the invention is not limited thereto.

Specific examples of cyan couplers that can be used in the present invention, including these, are described in JP-B-49-11572 and JP-A-61-61572.
-3142, 61-9652, 61-9653, 61-39045
Nos. 61-50136, 61-99141 and 61-105545.

The cyan dye-forming coupler represented by the formula [C-1] of the present invention is usually used in an amount of 1 × 10 5 per mol of silver halide.
^-3 mol to 1 mol, preferably 1 × 10 ^-2 mol to 8 × 10 ^-1 mol.

In the present invention, as the cyan coupler, a coupler represented by [C-1] and a 2,5-diacylamino cyan coupler are preferably used in combination.

As the 2,5-diacylaminophenol-based cyan coupler, those represented by the following general formula [C-2] are preferable.

In the formula, R ₁ represents an alkyl group or an aryl group. R ₂ represents an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group. R ₃ represents a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group. R ₃ may form a ring together with R ₁ . Z represents a hydrogen atom or an atom or group which can be removed by reaction with an oxidized form of an aromatic primary amine color developing agent.

In the cyan coupler represented by the general formula [C-2], the alkyl group represented by R _{1 has 1} to 32 carbon atoms.
Are preferred, and these may be linear or branched, and include those having a substituent.

The aryl group represented by R ₁ is preferably a phenyl group, including those having a substituent.

The alkyl group represented by R ₂ preferably has 1 to 32 carbon atoms. These alkyl groups may be linear or branched, and include those having a substituent.

The cycloalkyl group represented by R ₂ has 3 to 12 carbon atoms.
Are preferred, and these cycloalkyl groups include those having a substituent.

The aryl group represented by R ₂ is preferably a phenyl group, including those having a substituent.

The heterocyclic group represented by R ₂ is preferably a 5- to 7-membered heterocyclic group, including those having a substituent, and may be condensed.

R ₃ represents a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group, and the alkyl group and the alkoxy group include those having a substituent, and R ₃ is preferably a hydrogen atom.

Further, as the ring formed by R ₁ and R ₃ together, a 5- to 6-membered ring is preferable. And the like.

In the general formula (I), the atom or group capable of leaving by reaction with an oxidized form of the color developing agent represented by Z includes a halogen atom, an alkoxy group, an aryloxy group, an acyloxy group, a sulfonyloxy group, an acylamino group, Examples thereof include a sulfonylamino group, an alkoxycarbonyloxy group, an aryloxycarbonyloxy group, and an imide group (including those each having a substituent), preferably a halogen atom, an aryloxy group, and an alkoxy group.

Particularly preferred among the above-mentioned cyan couplers are those represented by the following general formula [C-2A].

In the formula, R _G1 represents a phenyl group substituted by at least one halogen atom, and these phenyl groups further include those having a substituent other than a halogen atom. R _G2 has the same meaning as R _{1 in} formula [C-2]. Z _G represents a halogen atom, an aryloxy group or an alkoxy group, including those having a substituent.

Hereinafter, typical specific examples of the cyan coupler represented by the general formula [C-2] are shown.

Further specific examples of the cyan coupler described above include, for example,
Japanese Patent Application No. 61-21853, pp. 26-35, JP-A-60-225
No. 155, page 7, lower left column to page 10, lower right column, JP-A-60-2
No. 22853, page 6, upper left column to page 8, lower right column;
9-185335, page 2, lower left column to page 9, upper left column, including 2,5-diacylamino cyan couplers,
It can be synthesized according to the methods described in these specifications and publications.

The cyan dye type coupler represented by the formula [C-2] of the present invention is usually used in an amount of 1 × 10 5 per mol of silver halide.
^-3 to 1 mol, preferably 1 × 10 ^-2 mol to 8 × 10 ^-1 mol.

When the cyan coupler represented by the general formula [C-1] and the cyan coupler represented by the general formula [C-2] are used in combination, the mixing ratio is preferably 1: 9 to 9: 1 in terms of molar ratio, and particularly preferably 7 to 7. : 3 to 3: 7 is preferred.

Next, the magenta coupler preferably used in the present invention is represented by the following general formula [M-1].

In the general formula [M-1], Z _m represents a group of nonmetallic atoms necessary for forming a nitrogen-containing heterocyclic ring, and the ring formed by Z _m may have a substituent.

X _m represents a hydrogen atom or a group capable of leaving by reaction with an oxidized form of a color developing agent.

Although no particular restriction on the substituent represented by R _m, typically, alkyl, aryl, anilino, acylamino, sulfonamido, alkylthio, arylthio, alkenyl, there may be mentioned the groups cycloalkyl or the like, the other A halogen atom and cycloalkenyl, alkynyl, heterocycle, sulfonyl, sulfinyl, phosphonyl,
Acyl, carbamoyl, sulfamoyl, cyano, alkoxy, aryloxy, heterocyclic oxy, siloxy, acyloxy, carbamoyloxy, amino, alkylamino, imide, ureido, sulfamoylamino, alkoxycarbonylamino, aryloxycarbonylamino, alkoxycarbonyl, Examples include aryloxycarbonyl, heterocyclic thio groups, spiro compound residues, bridged hydrocarbon compound residues, and the like.

The alkyl group represented by R _m preferably has 1 to 32 carbon atoms, and may be linear or branched.

The aryl group represented by R _m is preferably a phenyl group.

Examples of the acylamino group represented by R _m include an alkylcarbonylamino group and an arylcarbonylamino group.

Examples of the sulfonamide group represented by R _m include an alkylsulfonylamino group and an arylsulfonylamino group.

As the alkyl component and the aryl component in the alkylthio group and the arylthio group represented by R _m ,
Examples include an alkyl group and an aryl group represented by R _m .

The alkenyl group represented by R _m has 2 to 32 carbon atoms, and the cycloalkyl group has 3 to 12 carbon atoms, particularly 5 to 12 carbon atoms.
To 7 are preferable, and the alkenyl group may be linear or branched.

The cycloalkenyl group represented by R _m has 3 carbon atoms.
~ 12, especially 5-7 are preferred.

Examples of the sulfonyl group represented by R _m include an alkylsulfonyl group and an arylsulfonyl group; examples of the sulfinyl group include an alkylsulfinyl group and an arylsulfinyl group; and examples of the phosphonyl group include an alkylphosphonyl group and an alkoxyphosphonyl group. An acyloxy group such as an alkylcarbonyl group or an arylcarbonyl group; a carbamoyl group such as an alkylcarbamoyl group or an arylcarbamoyl group; a sulfamoyl group such as an alkyl group; An acyloxy group such as an alkylcarbonyloxy group or an arylcarbonyloxy group; a carbamoyloxy group such as an alkylcarbamo group; A ureido group such as an alkylureido group, an arylureido group, etc .; a sulfamoylamino group such as an alkylsulfamoylamino group, an arylsulfamoylamino group, etc .; The group is preferably a 5- to 7-membered ring, specifically, 2-furyl, 2-thienyl, 2-pyrimidinyl, 2-benzothiazolyl and the like; Those having a heterocyclic ring are preferred, and specifically, 3,4,5,6-tetrahydropyranyl-2-oxy group, 1-phenyltetrazole-
5-oxy group and the like; As the heterocyclic thio group, for example, a 5- to 7-membered heterocyclic thio group is preferable, for example, a 2-pyridylthio group, a 2-benzothiazolylthio group, a 2,4-diphenoxy-1,3, A 5-ethyltriazole-6-cyto group or the like; a siloxy group such as a triethylsiloxy group, a triethylsiloxy group, or a dimethylbutylsiloxy group; an imide group such as a succinimide group, a 3-heprimer succinimide group or a phthalimide group; Glutarimide group, etc .; Spiro compound residue as spiro [3.3] heprimer-yl etc .; Bridged hydrocarbon compound residue as bicyclo [2.2.1]
Heptan-1-yl, tricyclo [3.3.1.1 ^3,7 ] decan-1-yl, 7,7-dimethyl-bicyclo [2.2.1] heptan-1-yl and the like can be mentioned.

Examples of the group capable of splitting off upon reaction with an oxidation product of a color developing agent represented by X _m, for example, a halogen atom (chlorine atom, a bromine atom, and fluorine atom) and an alkoxy, aryloxy,
Heterocyclic oxy, acyloxy, sulfonyloxy, alkoxycarbonyloxy, aryloxycarbonyl,
Alkyloxalyloxy, alkoxyoxalyloxy, alkylthio, arylthio, heterocyclic thio, alkyloxythiocarbonylthio, acylamino, sulfonamide, nitrogen-containing heterocyclic ring linked by N atom, alkyloxycarbonylamino, aryloxycarbonylamino, carboxyl , (R _m1 ′ has the same meaning as R _m , Z ′ has the same meaning as Z, and R _m2 ′ and R _m3 ′ represent a hydrogen atom, an aryl group, an alkyl group or a heterocyclic group.) Although a group is mentioned, Preferably it is a halogen atom, especially a chlorine atom.

As the nitrogen-containing heterocyclic ring formed by Z _m or Z ', for example pyrazole ring, an imidazole ring, a triazole ring or a tetrazole ring, and examples of the substituent which may be the ring has the above R _m Those mentioned are mentioned.

More specifically, those represented by the general formula [M-1]
For example, they are represented by the following general formulas [M-II] to [M-VII].

In the above general formulas [M-II] to [M-VII], R _{m1 to} R
_m8 and X _m are as defined above R _m and X _m.

Among the general formulas [MI], preferred are those represented by the following general formula [M-VIII].

In the formula, R _m1 , X _m and Z _m1 are represented by the general formula [ _MI ]
Synonymous with R _m1 , X _m and Z _m .

Among the magenta couplers represented by the general formulas [M-II] to [M-VII], those particularly preferred are those represented by the general formula [MI]
I] is a magenta coupler represented by General formula [M-
Ring and the formula is formed by Z _m in I] [M-VI
The substituents which the ring formed by Z _m1 in (II) may have, and R _{m2 to} R _m8 in the general formulas (M-II) to (M-VI) represent the following general formula (M-IX) Is preferably represented by

The general formula [IX] -R ^m1 -SO ₂ -R in ^m2 formula R ^m1 is an alkylene group, R ^m2 represents an alkyl group, a cycloalkyl group or an aryl group.

The alkylene group represented by R ^m1 preferably has 2 or more carbon atoms in the straight-chain portion, more preferably 3 to 6, and may be straight-chain or branched.

The cycloalkyl group represented by R ^m2 is 5 to 6
Members are preferred.

When used for positive image formation, the substituents R _m and R _m1 on the heterocyclic ring are most preferably represented by the following general formula [M
-X].

In the formula, R _m9 , R _m10 and R _m11 have the same _{meanings as} the above R _m , respectively.

Further, two of the above R _m9 , R _m10 and R _m11 , for example, R _m9
And R _m10 include those bonded to form a saturated or unsaturated ring (eg, cycloalkane, cycloalkene, heterocyclic ring), and R _m11 is further bonded to the ring to form a bridged hydrocarbon compound residue May be.

Among the general formulas [ _MX ], preferred are (i) R _m9
When at least two of R _m11 are alkyl groups, (i
i) When one of R _{m9 to} R _m11 , for example, R _m11 is a hydrogen atom, and the other two R _m9 and R _m10 combine to form a cycloalkyl together with the root carbon atom.

Furthermore, a preferable case of (i) is a case where two of R _{m9 to} R _m11 are alkyl groups and the other one is a hydrogen atom or an alkyl group.

In the case of using the negative image formation, most preferably, the following formula as substituents R _m and R _m1 on the heterocyclic ring [M
-XI].

Formula [XI] R _m12 —CH ₂ — wherein R _m12 has the same _meaning as R _m described above.

_Preferred as R _m12 is a hydrogen atom or an alkyl group.

Hereinafter, typical specific examples of the compound of the general formula [M-1] will be shown.

In addition to the above typical examples, specific examples of the compound represented by the general formula [MI] include compounds described on pages 66 to 122 of Japanese Patent Application No. 61-9791. No.1 in
-4, 8-17, 14-24, 26-43, 45-59, 61-104, 106
To 121, 123 to 162, and 164 to 223.

In addition, the above coupler is used in the Journal of the Chemical Societe
y), Perkin I (1977), 2047-2052, U.S. Pat. No. 3,725,067, JP-A-59-99437, and JP-A-59-42.
No. 045, No. 59-162548, No. 59-171956, No. 60
No. 33552, 60-43659, 60-172292 and 60-43659, and the like.

The magenta coupler represented by the general formula [MI] is used in an amount of usually 1 × 10 ⁻³ mol to 1 mol, preferably 1 × 10 ⁻² mol to 8 × 10 ⁻⁸ per mol of silver halide. Is preferred.

The coupler represented by the general formula [MI] can be used in combination with another type of magenta dye-forming coupler.

It is also a preferred embodiment to use a polymer coupler in the present invention. Japanese Patent Application No. 59 as a polymer coupler
P-2, P-5, P-13, P-14, P-17, P-22 described in -95611
And P-23 are preferably used, and the following polymer couplers are also useful for achieving the effects of the present invention.

When the color photographic light-sensitive material is a negative light-sensitive material, preferred yellow couplers include benzoylacetanilide-based yellow couplers.

The benzoylacetanilide-based yellow coupler includes any benzoylacetanilide derivative, and preferred are compounds represented by the following general formula [YB-I].

In the formula, R _{1 to} R ₇ and W are a hydrogen atom or a substituent, and preferably R ₁ , R ₂ and R ₃ include both the same and different, each of which is a hydrogen atom, a halogen atom, an alkyl group, Represents an aryl group, an alkoxy group, an acylamino group, a carbamoyl group, an alkoxycarbonyl group, a sulfonamide group, or a sulfamoyl group.

R ₄ , R ₅ , R ₆ and R ₇ include both the same and different, and preferably each represents a hydrogen atom, an alkyl group, an alkoxy group, an aryloxy group, an acylamino group or a sulfonamide group.

W preferably represents a halogen atom, an alkyl group, an alkoxy group, an aryloxy group or a dialkylamino group.

X ₁ represents a hydrogen atom or a removable group, and examples of the removable group include a halogen atom, an alkoxy group, an aryloxy group, an acyloxy group, an alkylthio group, an arylthio group, a heterocyclic thio group, a saturated or Examples thereof include a saturated 5- or 6-membered nitrogen-containing heterocyclic group. Particularly preferred groups are represented by general formulas [YB-II] and [YB-III].

Y ₁ represents a nonmetallic atom group necessary for forming a 5- to 6-membered ring, and the nonmetallic atom group includes those having a substituent.

General formula [YB-III] -O-Ar Ar represents an aryl group, and the aryl group includes those having a substituent.

Hereinafter, specific examples of the benzoylacetanilide-based yellow coupler will be described, but the present invention is not limited thereto.

These benzoylacetanilide yellow couplers according to the present invention are described in U.S. Pat.
No. 3,891,445, JP-B-51-10783, JP-A-48-108
73147, 50-6341, 51-102636, 52-11521
No. 9, 54-21448, 56-95237, 59-159163
No. 59-174838, No. 59-206835, JP-A-1-1875
No. 60, No. 1-207748, No. 1-207749, No. 1-214848
No. 1-227152, 1-231050, 1-295256
Nos. 1-309057, 1-341240, 1-316744
And those described in JP-A-1-316745 and synthesized by the method described.

The benzoylacetanilide-based yellow coupler according to the present invention may be used in two or more kinds, or may be used in combination with other yellow couplers.

In order to add a yellow coupler to a light-sensitive material, an oil-in-water type emulsification dispersion method using a water-insoluble high-boiling organic solvent or an alkali dispersion method adding as an alkaline solution is used depending on the physical properties (eg, solubility) of the yellow coupler. Various methods can be used, such as a latex dispersion method, a solid dispersion method of directly adding a fine solid, and the like.

The amount of the yellow coupler to be added is usually 1.0 × 10 ⁻³ mol to 1.0 mol, preferably 5.0 mol / mol of silver halide in total.
The range is from × 10 ^-3 mol to 8.0 × 10 ^-1 mol.

The benzoylacetanilide-based yellow coupler according to the present invention is usually contained in a blue-sensitive silver halide emulsion layer, but depending on the purpose, such as green-sensitive or red-sensitive,
It may be contained in a silver halide emulsion layer having a color sensitivity other than blue.

When the color photographic light-sensitive material is a positive-working light-sensitive material, preferred yellow couplers include those represented by the following general formula [Y-1].

In the above formula, R ₁ represents an alkyl group or a cycloalkyl group, R ₂ represents an alkyl group, a cycloalkyl group, an acyl group or an aryl group, R ₃ represents a group that can be substituted on a benzene ring, and n represents 0 Or 1; Y represents a monovalent ballast group; Z represents a hydrogen atom or an atom or group capable of leaving during coupling.

In the general formula [Y-1], the alkyl group represented by R ₁ may be linear or branched, and includes, for example, a methyl, ethyl, isopropyl, t-butyl, dodecyl group and the like. These alkyl groups include those further having a substituent. Examples of the substituent include a halogen atom and groups such as aryl, alkoxy, aryloxy, alkylsulfonyl, acylamino, alkoxy, and hydroxy.

Examples of the cycloalkyl group represented by R ₁ include cyclopropyl, cyclohexyl, and adamantyl group.

R ₁ is preferably a branched alkyl group.

As the alkyl group and cycloalkyl group represented by R ₂
Examples of the same group as R ₁ include, and examples of the aryl group include a phenyl group. The alkyl group, cycloalkyl group and aryl group represented by R ₂ include those having the same substituent as R ₁ . Examples of the acyl group include an acetyl, propionyl, butyryl, hexanoyl, benzoyl group and the like.

R ₂ is preferably an alkyl group or an aryl group, and more preferably an alkyl group.

R ₃ is not particularly limited as long as it is a group capable of substituting for a benzene ring, and specifically, a halogen atom (for example, chlorine atom), an alkyl group (for example, ethyl, i-propyl, t-butyl group), an alkoxy group (for example, Methoxy group), aryloxy group (eg, phenyloxy group), acyloxy group (eg, methylcarbonyloxy, benzoyloxy group), acylamino group (eg, acetamido, phenylcarbonylamino group), carbamoyl group (eg, N-methylcarbamoyl, N- Phenylcarbamoyl group), alkylsulfonamide group (eg, ethylsulfonylamino group), arylsulfonamide group (eg, phenylsulfonylamino group), sulfamoyl group (eg, N-propylsulfamoyl, N-phenylsulfamoyl group) and imide Group (for example, koha Acid imide, glutarimide group).

In the general formula [Y-1], Z represents a group capable of leaving during a coupling reaction with an oxidized form of a developing agent, and for example, a group represented by the following general formula [Y-2] or [Y-3] Represent.

—OR ₁₀ [Y-2] In the general formula [Y-2], R ₁₀ represents an aryl group or a heterocyclic group including those having a substituent.

In the general formula [Y-3], Z represents a nonmetallic atom group necessary for forming a 5- to 6-membered ring in cooperation with a nitrogen atom. Here, the atomic groups necessary to form a non-metallic atomic group include, for example, methylene, methine, substituted methine, —NH—, —N ＝, —O—, —S—, —SO ₂ — and the like.

The yellow dye-forming coupler represented by the above general formula [Y-1] of the present invention generally has 1 × per mole of silver halide.
10 ^-3 mol to 1 mol, preferably 1 × 10 ^-2 mol to 8 × 10 ^-1
It can be used in the molar range.

Next, specific examples of the yellow coupler represented by the above general formula [Y-1] are shown.

The silver halide color photographic light-sensitive material used in the present invention, particularly a negative light-sensitive material, is a compound which releases a bleaching accelerator by reacting with an oxidized form of a color developing agent in at least one layer of a silver halide emulsion layer (hereinafter referred to as a BAR compound). ), The effects of the present invention are more favorably achieved.

Preferred examples of the BAR compound include compounds represented by the following general formulas [BAR-A] and [BAR-B].

In the formula, Cp represents a coupler residue capable of performing a coupling reaction with an oxidized form of a color developing agent, * represents a coupling position of the coupler, TIME represents a timing group, and m and l represent 0 or 1, respectively. represents, R ₁ is (preferably an alkylene group having 1 to 8 carbon atoms) bonded group represents, R ₂ is a hydrogen atom, a cyano group, -COR ₃ -csr _3, A heterocyclic group (R ₃ represents an alkyl group or an aryl group; R ₄ ,
R ₅ and R ₆ represent a hydrogen atom, an alkyl group, or an aryl group. ).

Rb ₁ is a divalent aliphatic group having 1 to 8 carbon atoms, or (Wherein L represents a divalent aliphatic group having 1 to 8 carbon atoms or a phenylene group), and Rb ₂ represents a water-soluble group or a precursor thereof.

In the above formula, the coupler residue represented by Cp includes, in the general formula, a residue that forms a yellow, magenta or cyan dye, and a residue that forms a substantially colorless product.

Representative examples of the coupler residue represented by Cp as a yellow coupler residue include, for example, U.S. Pat.
No. 298,443, No. 2,407,210, No. 2,875,057, No.
No. 3,048,194, No. 3,265,506, No. 3,447,928 and Farbukplaaine Litterat Ulverzicht Agfa Mittling (Band II) "｛Farbkup
p-lereine Literaturuversiecht Agfa Mitteilung (Ba
ndII) @ 112-126 (1961). Of these, acylacetanilides, for example, benzoylacetanilide and pivaloylacetanilide are preferred.

As a typical magenta coupler residue,
For example, U.S. Patent Nos. 2,369,489, 2,343,703,
No. 2,311,182, No. 2,600,788, No. 2,908,573, No. 3,062,653, No. 3,152,896, No. 3,519,429,
No. 3,725,067, No. 4,540,654, JP-A-59-162548
And Agfa Mitteilung (Band II), pp. 126-156 (19
61)). Of these, pyrazolone or pyrazoloazole (eg, pyrazoloimidazole, pyrazolotriazole, etc.) are preferred.

Representative examples of the cyan coupler residue include, for example, U.S. Pat.Nos. 2,367,531, 2,423,730 and 2,
No. 472,293, No. 2,772,162, No. 2,395,826, No.
No. 3,002,836, No. 3,034,892, No. 3,041,236, No. 4,666,999 and Agfa Mitteilung (Band II) 1
There are those described on pages 56 to 175 (1961).
Of these, phenols and naphthols are preferred.

Representative coupler residues which form a substantially colorless product include, for example, GB 861,138, U.S. Pat.Nos. 3,632,345, 3,928,041, and
Nos. 3,958,993 and 3,961,959. Of these, cyclic carbonyl compounds are preferred.

The timing group represented by TIME is the bleach accelerator group. A group that allows timed release from Cp, including the rate of reaction between Cp and the oxidized form of the color developing agent, released from Cp -TIME-S-Rb ₁ -Rb ₂ diffusion rate, and the rate of release of the bleach accelerator group may contain a group capable of control. Representative timing groups include U.S. Pat.
No. 962, JP-A-57-154234, which release a bleaching accelerator group by an intramolecular nucleophilic conversion reaction disclosed in JP-A-57-56837, JP-A-56-114946, and JP-A-57-154234. Examples include those that release a bleaching accelerator group by an electron transfer reaction along a conjugated chain disclosed in a gazette or the like. In addition, JP-A-57-188035, JP-A-58-98728, JP-A-59-206834,
No. 60-7429, No. 60-214358, No. 50-225844, No. 60
-229030, 60-233649, 60-237446, 60-
The timing group disclosed in Japanese Patent No. 237447 is exemplified.

In -S-Rb ₁ -Rb ₂ is one of the bleach accelerator group,
Rb ₁ is a divalent aliphatic group having 1 to 8 carbon atoms, or (Wherein L represents a divalent aliphatic group having 1 to 8 carbon atoms or a phenylene group), and is more preferably represented by the following formula.

In the formula, R ₃ ′ and R ₄ ′ each represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and nb represents 1 to 8. When nb is 2 or more, R ₃ ′ and R ₄ ′ are the same and may be different.

The alkyl group represented by R ₃ ′ and R ₄ ′ may be linear or branched, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group. And ter-butyl groups. General formula [BAR-A]
As preferred groups for R _{1 in} the above, shown as preferred groups for Rb ₁ above And the groups having the same meanings as above.

Preferred Rb ₁ are described below.

Water solubilizing group represented by Rb ₂ or listed below preferred as a precursor.

(Wherein, R ₅ ′ and R ₆ ′ each represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.) Particularly preferred as a bleaching accelerator group represented by —S—Rb ₁ —Rb ₂ Is It is.

In the general formulas [BAR-A] and [BAR-B], the yellow coupler residue represented by Cp includes the following general formula [II]
And those represented by [III] are preferred.

In the general formulas (II) and (III), R ₇ and R ₈ represent an alkyl, cycloalkyl, aryl, hetero ring or halogen atom, and the alkyl, cycloalkyl, aryl, and hetero ring are an oxygen atom, a nitrogen atom. , May be bonded via a sulfur atom. Further, the above alkyl, cycloalkyl, aryl and heterocycle may be bonded via the following bonding groups. That is, acylamino, carbamoyl, sulfonamide, sulfamoyl, sulfamoylcarbonyl, carbonyloxy, oxycarbonyl, ureido, thioureido, thioamide, sulfone,
The bond may be formed through sulfonyloxy or the like. The above-mentioned alkyl, cycloalkyl, aryl and heterocycle further include those having the substituents described below. That is, examples of the substituent include a halogen atom, nitro,
Cyano, alkyl, alkenyl, cycloalkyl, aryl, alkoxy, aryloxy, alkoxycarbonyl, aryloxycarbonyl, carboxy, sulfo, sulfamoyl, carbamoyl, acylamino, ureido, urethane, sulfonamide, heterocycle, arylsulfonyl, alkylsulfonyl, arylthio , Alkylthio, alkylamino, anilino, hydroxy,
Examples include imide and acyl. R ₇ and R ₈ are each 2
When there is more than one, they include both the same and different.

In the general formulas [BAR-A] and [BAR-B], the magenta coupler residue represented by Cp is represented by the following general formula [I
V], [V], [VI] and [VII] are preferred.

R _7, R ₈ in the above general formula [IV] - [VII] the general formula (II) has the same meaning as R _7, R ₈ of (III).

In the general formulas (BAR-A) and (BAR-B), as a cyan coupler residue represented by Cp, the following general formula (VIII):
Those represented by [IX] and [X] are preferred.

In the above [VIII] to [X], R ₇ and R ₈ are represented by the general formula [I
It is the same as R ₇ and R ₈ in [I] and [III].

In the general formulas [BAR-A] and [BAR-B], coupler residues forming a substantially colorless product represented by Cp are represented by general formulas [XI] to [XIV]. Is preferred.

In the formula, R ₉ represents a hydrogen atom, an alkyl group, an aryl group, a halogen atom, an alkoxy group, an acyloxy group, or a heterocyclic group, and X represents an oxygen atom or ＮN—R ₁₀ . R ₁₀ represents an alkyl group, an aryl group, a hydroxy group, an alkoxy group or a sulfonyl group. Z represents a group of nonmetallic atoms necessary for forming a 5- to 7-membered carbocycle (eg, indanone, cyclopentanone, cyclohexanone, etc.) or a heterocycle (eg, pepyridone, pyrrolidone, hydrocarbostyril, etc.).

Wherein, R ₉ R ₉ and X in the general formula [XI] and X
And R ₁₁ represents an alkyl group, an aryl group, a heterocyclic group, a cyano group, a hydroxy group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, an alkylamino group, a dialkylamino group, or an anilino group.

In the formula, R ₁₂ and R ₁₃ are the same or different, and include both an alkoxycarbonyl group, a carbamoyl group, an acyl group, a cyano group, a formyl group, a sulfonyl group, a sulfinyl group, a sulfamoyl group, an ammonium mill group or Represents A is a 5- to 7-membered heterocycle together with a nitrogen atom (for example, phthalimide, triazole, tetratisol, etc.)
Represents a group of nonmetallic atoms necessary to form

In the formula, R ₁₄ represents, for example, an alkyl group, an aryl group, an anilino group, an alkylamino group or an alkoxy group, and B represents an oxygen atom, a sulfur atom or a nitrogen atom.

TIME useful in practicing the present invention include, but are not limited to, those represented by the following general formulas [XV], [XVI], and [XVII].

In the formula, X represents an atomic group necessary to complete a benzene ring or naphthalene ring which may have a substituent.

And in general formulas [BAR-A] and [BAR-B], Cp
And R ₁₅ , R ₁₆ and R ₁₇ represent a hydrogen atom, an alkyl group or an aryl group. Also, The group is substituted ortho or para to Y and is attached to the oxygen atom of the bleach accelerator group.

In the formula, Y, R ₁₅ and R ₁₆ have the same meanings as in general formula [XV]. R ₁₈ is, for example, a hydrogen atom, an alkyl group, an aryl group,
An acyl group, a sulfonyl group, an alkoxycarbonyl group, a heterocyclic residue, R ₁₉ is a hydrogen atom, an alkyl group, an aryl group, a heterocyclic residue, an alkoxy group, an amino group, an acid amide group, a sulfonamide group, a carboxy, It represents an alkoxycarbonyl group, a carbamoyl group, cyano or the like. In addition, this timing group is represented by Y as in the general formula (XV), and at the coupling position of the coupler residue represented by Cp in the general formulas (BAR-A) and (BAR-B), Bond to the oxygen atom of the bleach accelerator group.

Next, an example of a timing group which releases a bleaching accelerator group by an intramolecular nucleophilic substitution reaction is shown by a general formula [XVII].

In the formula, Nu is a nucleophilic group having an electron-rich oxygen, sulfur or nitrogen atom, and represented by the general formulas [BAR-A] and [BAR
-B], it is bonded to the coupling position of the coupler residue represented by Cp. E is an electrophilic group having a carbonyl group, a thiocarbonyl group, a phosphinyl group, or a thiophosphinyl group having insufficient electrons, and is bonded to an oxygen atom to the bleaching accelerator group. X is a steric relation between Nu and E, and after Nu is released from the coupler residue represented by Cp in the general formulas [BAR-A] and [BAR-B], a three-membered ring to 7 It is a linking group that can undergo an intramolecular nucleophilic reaction with the formation of a member ring and thereby release a bleach accelerator.

Representative specific examples of the timing group include the following.

Hereinafter, specific examples of the BAR compound that can be used in the present invention will be described, but the present invention is not limited to these examples.

In the method for processing a silver halide color photographic light-sensitive material of the present invention, the silver halide emulsion used in the negative light-sensitive material is a silver halide grain composed of two or more phases having different silver iodide contents. Further, it is preferable that the emulsion is a silver halide emulsion containing silver halide grains whose average silver iodide content is higher than the silver iodide content of the peripheral phase of the grains.

The fact that the average silver iodide content of the grains is higher than the silver iodide content of the outer phase of the grains can be measured by the following method.

When the average value of grain size / grain thickness is 5
In the case of an emulsion containing silver halide grains less than
When the average silver iodide content (J ₁ ) determined by X-ray analysis and the silver iodide content (J ₂ ) of the grain surface determined by X-ray photoelectron spectroscopy are compared, the relationship of J ₁ > J ₂ is satisfied. Is what you do.

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

 X-ray photoelectron spectroscopy will be described.

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

For the measurement by the X-ray photoelectron spectroscopy, an ESCA / SAM560 type manufactured by PHI was used as an apparatus, and the excitation X-ray was Mg-Kα ray,
X-ray source voltage 15KV, X-ray source current 40mA, pass energy 50eV
It is performed under the following conditions.

Ag3d, Br3d, I3d3 / 2 electrons are detected to determine the surface halide composition.

The calculation of the composition ratio is performed by the relative sensitivity coefficient method using the integrated intensity of each peak. By using 5.10, 0.81, and 4.592 as Ag3d, Br3d, and I3d3 / 2 relative sensitivity coefficients, respectively,
The composition ratio is given in atomic percent.

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. Monodisperse silver halide emulsion is ± 20% around the average grain size
The weight of silver halide contained within the particle size range of 60% or more of the total weight of silver halide grains, preferably
It is 70% or more, more preferably 80% or more.

Here, the average particle size is the frequency of particles having a particle size γi.
product ni × .gamma.i ³ between ni and .gamma.i ³ is defined as the particle size .gamma.i when the maximum (three significant figures, the minimum digit is ON 4 discard 5).

The particle size referred to here is the diameter of a spherical silver halide grain, or the diameter of a projected image converted to a circular image of the same area for a particle having a shape other than spherical.

The particle size can be obtained, for example, by photographing the particle with an electron microscope at a magnification of 10,000 to 50,000 times and actually measuring the particle diameter on the print or the area at the time of projection (the number of measured particles is zero). It is assumed that there are at least 1000 discriminations.) Particularly preferred highly monodispersed emulsions of the present invention are: Is less than 20% of the distribution defined by
It is more preferably at most 15%.

Here, the average particle size and the particle size standard deviation are determined from γi defined above.

In the case where the silver halide emulsion is a tabular silver halide emulsion having an average value of grain size / grain thickness of 5 or more, the fluorescence X
Average silver iodide content (J ₁ ) determined by X-ray analysis and measured on a silver halide crystal 80% or more away from the center with respect to the grain size direction of silver halide grains using X-ray microanalysis. When the average value (J ₃ ) of the measured values of the silver iodide content is compared, the relationship of J ₁ > J ₃ is satisfied.

The X-ray microanalysis method will be described. Silver halide particles are dispersed in an electron microscope observation grid in which an energy dispersive X-ray analyzer is installed in an electron microscope, and the magnification is set so that one particle enters the CRT visual field by cooling with liquid nitrogen, and AgLα, Integrate the intensity of ILα radiation. ILα / AgL
The silver iodide content can be calculated using the intensity ratio of α and the calibration curve prepared in advance.

In a tabular silver halide emulsion having an average value of grain size / grain thickness of 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.

That the average value of the thickness of the grain diameter / grain silver iodide content of the grain surface by X-ray photoelectron spectroscopy in the silver halide emulsion of the present invention is less than 5 (J ₂₎ is 6-0 moles It is preferably from 5 to 0 mol%, more preferably from 4 to 0.01 mol%.

In the tabular silver halide emulsion of the present invention having an average value of the grain size / grain thickness of 5 or more, the tabular silver halide emulsion of the present invention is separated from the center by 80% or more with respect to the grain size direction by the X-ray microanalysis method. the average value of the measurements of silver iodide content measured on the silver halide crystals (J ₃₎ is preferably 6 to 0 mol%, more preferably from 5 to 0 mol%, particularly preferably 4 ~ 0.01 mol%. The average thickness of the tabular silver halide grains is preferably 0.5 to 0.01 μm,
Particularly preferably, it is 0.3 to 0.05 μm. The average grain size of the silver halide grains contained in the tabular silver halide emulsion is 0.5
To 30 μm, more preferably 1.0 to 20 μm.

The silver halide emulsion having an average value of the aforementioned grain size / grain thickness of less than 5 is preferably monodisperse,
It is preferably a shell type. In the tabular silver halide emulsion having an average value of the grain size / grain thickness of 5 or more, silver iodide is preferably localized in the center of the grain.

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

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

The proportion occupied by the shell portion of the core / shell type silver halide grains is preferably 10 to 80% by volume, more preferably 15 to 80%.
It is 70%, particularly preferably 20-60%.

The ratio of core is 10 to 80% by volume
And more preferably 20 to 50%.

The difference in the content between the core portion having a high silver iodide content and the shell portion having a low silver iodide content in a silver halide grain may have a sharp boundary, or may be a continuously changing boundary that is not always apparent. There may be. Those having an intermediate phase having a silver iodide content between the core and the shell between the core and the shell are also preferably used.

In the case of the 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 whole grains. The difference between the silver iodide content of the shell and the intermediate layer, the difference between the silver iodide content of the intermediate layer and the core is preferably 3 mol% or more, and the difference between the silver iodide content of the shell and the core is preferably 6 mol% or more.

The core / shell type silver halide emulsion is preferably silver iodobromide, and the average silver iodide content is preferably 4 to 20 mol%, more preferably 5 to 15 mol%. Further, silver chloride may be contained as long as the effects of the present invention are not impaired.

The core / shell type silver halide emulsion is described in JP-A-59-17753.
5, 60-138538, 59-52238, 60-143331, 60-
It can be produced by a known method disclosed in, for example, 35726 and 60-258536.

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

In such a case, the halogen composition of the seed grains may be any composition such as silver bromide, silver iodobromide, silver chloroiodobromide, silver chlorobromide, and silver chloride. Silver iodobromide or silver bromide of 10 mol% or less is preferred.

The ratio of the seed grains to the total silver halide is 50 by volume.
% Or less, and particularly preferably 10% or less.

The distribution state of silver iodide in the core / shell type silver halide grains can be detected by various physical measurement methods, and is described, for example, in the Photographic Society of Japan, Abstracts of 1981 Annual Meeting. Such luminescence can be measured by low-temperature luminescence measurement or X-ray diffraction.

The core / shell type silver halide grains may be normal crystals such as cubic, tetradecahedral, and octahedral, may be composed of twins, or may be a mixture thereof, but may be normal crystals. preferable.

In a tabular silver halide emulsion having an average value of grain size / grain thickness of 5 or more and silver iodide localized at the center of the grain, the high iodine content phase at the center is the total volume of the grain. 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 30 mol%.
Is preferred. The low iodine content phase surrounding the high iodide content phase at the center (peripheral portion) is composed of silver iodobromide having a silver iodide content of 0 to 10 mol%, more preferably 0.1 to 6.0 mol%. Is preferred.

A tabular silver halide emulsion in which silver iodide is localized at the center can be obtained by a known method disclosed in JP-A-59-99433 and the like.

In the method for processing a silver halide color photographic light-sensitive material of the present invention, the average silver iodide content of all silver halide emulsions in the negative-working silver halide photographic light-sensitive material is preferably 0.1 to 15 mol%, It is more preferably from 0.5 to 12 mol%, particularly preferably from 1 to 6 mol%.

The average grain size of all silver halide emulsions in the negative silver halide color light-sensitive material is preferably 2.0 μm or less, more preferably 0.1 to 1.0 μm or less, and particularly preferably 0.2 to 0.6 μm.
It is.

Total dry film thickness of all hydrophilic colloid layers of silver halide color photographic light-sensitive materials for negative images (hereinafter referred to as emulsion film thickness)
The lower limit of is limited by the contained silver halide emulsion, coupler, oil agent, additive and the like, and the preferred thickness of the emulsion surface is 5 μm to 18 μm, more preferably 10 μm to 16 μm.
μm. Further, the thickness is preferably 14 μm or less from the outermost surface of the emulsion surface to the lower end of the emulsion layer closest to the support, and 10 μm from the emulsion layer which is different in color sensitivity from the emulsion layer to the lower end of the emulsion layer next to the support. The following is preferred.

As a method for reducing the thickness of the negative color light-sensitive material, there is a method of reducing the amount of hydrophilic colloid as a binder. The purpose is to retain the minute oil droplets of couplers dissolved in silver halide and high boiling point solvent, to prevent fog rise due to mechanical stress, and to prevent color turbidity due to diffusion of oxidized developing agent between layers. Since the hydrophilic colloid is added in the above, the weight can be reduced as long as the purpose is not impaired.

As another method of thinning, there is a method of using a coupler having high coloring property.

Other methods of thinning include a method of reducing the amount of a high-boiling solvent, and a method of thinning an intermediate layer by adding a scavenger of an oxidized developing agent to an intermediate layer having different color sensitivity. Can be

The sum of the silver halide is preferably from 6.5 g / m ² or less contained in the photosensitive silver halide emulsion contained in the total emulsion layer of negative silver halide color photographic light-sensitive material, more preferably 2.5～6.0G / m ² , more preferably 3.0 to 5.5 g / m ² , particularly preferably 3.5 to 5.0 g / m ² .

The total hydrophilic protective colloid layer coated on the emulsion layer side on the support of the silver halide color photographic light-sensitive material for negative images, the swelled film thickness when developed is 180% to 350% of the film thickness when dried. Preferably, it is particularly preferably from 200% to 300%.

Techniques for adjusting the swelled film thickness are well known to those skilled in the art, and can be performed, for example, by appropriately selecting the amount and type of the hardener.

Examples of the hardener include aldehydes and aziridines (for example, PB Report, 19,921, U.S. Pat. Nos. 2,950,197 and 2,9
Nos. 64,404, 2,983,311 and 3,271,175,
JP-B-46-40898 and JP-A-50-91315), isoxazoles (for example, US Pat.
No. 609), epoxy type (for example, US Pat. No. 3,047,394, West German Patent 1,085,663, British Patent 1,03
3,518, JP-B-48-35495), vinylsulfones (for example, PB Report 19,92)
0, West German Patents 1,100,942, 2,337,412, 2,545,722
Nos. 2,635,518, 2,742,308, 2,749,260, British Patent 1,251,091, Japanese Patent Application No. 45-54236, and 48-110996
, U.S. Pat. Nos. 3,539,644 and 3,490,911), acryloyl series (for example, Japanese Patent Application No. 48-27).
949, U.S. Pat. No. 3,640,720), carbodiimide-based (for example, U.S. Pat.
Nos. 4,043,818, 4,061,499
46-38715, Japanese Patent Application No. 49-15095, triazines (for example, West German Patent 2,410,973,
No. 2,553,915, U.S. Pat.No. 3,325,287, those described in JP-A No. 52-12722, polymer type (for example, British Patent 822,061, U.S. Pat. No. 3,623,878, and 3,39)
Nos. 6,029 and 3,226,234, JP-B-47-18578
Nos. 18579 and 47-48896), and other hardening agents of maleimide type, acetylene type, methanesulfonic acid ester type, and (N-methylol type) are used alone or in combination. it can. Examples of useful combination techniques include, for example, West German Patents 2,447,587, 2,505,746,
No. 514,245, U.S. Pat.Nos. 4,047,957, 3,832,181,
No. 3,840,370, JP-A-48-43319, JP-A-50-63
Nos. 062, 52-127329, and JP-B-48-32364.

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

Swelling degree measurement solution 4-Amino-3-methyl-N-ethyl-N- (β-hydroxyethyl) -aniline sulfate 4.75 g Sodium sulfite anhydrous 4.25 g Hydroxylamine 1/2 sulfate 2.0 g Anhydrous potassium carbonate 37.5g Sodium bromide 1.3g Nitrilotriacetic acid trisodium salt (monohydrate) 2.5g Potassium hydroxide 1.0g Add water to make 1

The measurement of the swollen film thickness can be performed by, for example, A. Green and G. I. Levenson, Journal of Photographic Science (J. Photogr. Sci.), 2
0 , 205 (1972).

The dry film thickness means a film thickness measured at 23 ° C. and 55% humidity control. For each film thickness, a cross section of the dried sample is magnified and photographed with an operation electron microscope, and the film thickness of each layer is measured.

Examples of the above-mentioned all-hydrophilic protective colloid layer include a blue-sensitive, green-sensitive, and red-sensitive silver halide emulsion layer having at least one layer each as described above, and a protective layer and an antihalation layer which are applied as necessary. , A yellow filter layer, an intermediate layer and the like.

The layer constitution of the silver halide color photographic light-sensitive material for negative images which can particularly exert the effect of the present invention is as follows: from the support, a colloidal silver antihalation layer (interlayer), a red-sensitive layer (interlayer)
Green-sensitive layer (intermediate layer) Colloidal silver yellow filter layer Blue-sensitive layer (intermediate layer) Coated with a protective layer Further, from the support, colloidal silver antihalation layer (intermediate layer) Red-sensitive layer (intermediate layer) Green-sensitive layer (Intermediate layer) Blue-sensitive layer (intermediate layer) Red-sensitive layer (intermediate layer) Green-sensitive layer (colloidal silver yellow filter layer) Blue-sensitive layer (intermediate layer) Protective layer is applied.

Note that the layers in parentheses may be omitted. Each of the red-sensitive layer, green-sensitive layer, and blue-sensitive layer is preferably divided into low-sensitivity and high-sensitivity layers. In addition, Tokubiko 49-
As disclosed in JP-A-51-49027, at least one of a red-sensitive layer, a green-sensitive layer and a blue-sensitive layer described in JP-A-15495 is divided into three partial layers. Layer composition in which a high-speed emulsion layer unit and a low-speed emulsion layer unit are separated, and West German Patent Publication Nos. 2,622,922, 2,622,923, and 2,62.
Examples of the layer structure include those described in 2,924, 2,704,826 and 2,704,797.

In the present invention, JP-A-57-177551 and JP-A-59-177551
It is also possible to apply the layer configurations described in JP-A-177552 and JP-A-59-180555.

These silver halide emulsions include active gelatin; sulfur sensitizers such as allylthiocarbamide, thiourea and cystine; selenium sensitizers; reduction sensitizers such as stannous salts and thiourea dioxide. Noble metal sensitizers, such as gold sensitizers, specifically, potassium aurithiocyanate, potassium chloroaurate, 2-aurothio-3-methylbenzothiazolium chloride, and the like, or, for example, ruthenium, palladium, platinum, rhodium And sensitizers of water-soluble groups such as iridium, specifically, ammonium chloroparadate, potassium chloroplatinate, and sodium chloroparadate (some of these may be sensitizers or fog inhibitors depending on the size of the sensitizers). Etc.) alone or in combination as appropriate (for example, a gold sensitizer and a sulfur sensitizer). Combination, combination and the like of the gold sensitizer and a selenium sensitizer) may be chemically sensitized with.

The silver halide emulsion is chemically ripened by adding a sulfur-containing compound, and before, during or after the ripening, at least one of a nitrogen-containing heterocyclic compound having at least one hydroxytetrazaindene and a mercapto group. One kind may be included.

The silver halide is added with an appropriate sensitizing dye in an amount of 5 × 10 ^{−8 to} 3 × 10 ⁻³ mol per mol of silver halide in order to impart photosensitivity to a desired photosensitive wavelength range. It may be sensitized. Various sensitizing dyes can be used, and one or a combination of two or more sensitizing dyes can be used. Examples of the sensitizing dye advantageously used in the present invention include the following.

That is, examples of sensitizing dyes used in blue-sensitive silver halide emulsions include, for example, West German Patent 929,080 and U.S. Pat.
No. 58, No. 2,493,748, No. 2,503,776, No. 2,519,001
Nos. 2,912,329, 3,656,959, 3,672,897,
Nos. 3,694,217, 4,025,349, 4,046,572, British Patent 1,242,588, Japanese Patent Publication Nos. 4414030 and 52-24844, and the like. As sensitizing dyes used in green-sensitive silver halide emulsions, for example, U.S. Pat.Nos. 1,939,201, 2,072,908, and 2,739,149
No. 2,945,763, British Patent No. 505,979, and the like, there can be mentioned cyanine dyes, merocyanine dyes or complex cyanine dyes as typical examples. Further, as sensitizing dyes used in red-sensitive silver halide emulsions, for example, U.S. Patent Nos. 2,269,234 and 2,270,378
And cyanine dyes, merocyanine dyes and composite cyanine dyes described in JP-A Nos. 2,442,710, 2,454,629, and 2,776,280 can be mentioned as typical examples. Further, U.S. Pat.Nos. 2,213,995 and 2,4
Cyanine dyes, merocyanine dyes or composite cyanine dyes described in, for example, U.S. Pat. Nos. 93,748 and 2,519,001 and West German Patent 929,080 can be advantageously used in a green-sensitive silver halide emulsion or a red-sensitive silver halide emulsion.

These sensitizing dyes may be used alone or in combination.

If necessary, optical sensitization may be performed in a desired wavelength region by a spectral sensitization method using a single or combination of cyanine or merocyanine dyes.

Representative examples of particularly preferred spectral sensitization methods include, for example, JP-B-43-4936 which relates to a combination of benzimidazolocarbocyanine and benzoxazolocarbocyanine.
No. 43-22884, No. 45-18433, No. 47-37443,
Nos. 48-28293, 49-6209, 53-12375, JP
52-23931, 52-51932, 54-80118, 58-1
Nos. 53926, 59-116646, 59-116647 and the like.

Examples of a combination of a carbocyanine having a benzimidazole nucleus and another cyanine or merocyanine include, for example, JP-B-45-25831 and JP-B-47-11114.
No. 47-25379, No. 48-38406, No. 48-38407,
JP-A-54-34535, JP-A-55-1569, JP-A-50-33220, JP-A-50-33220
Nos. 50-38526, 51-107127, 51-115820, 51
Nos. -135528, 52-104916, and 52-104917.

Further, as for the combination of benzoxazolocarbocyanine (oxa-galcocyanine) with other carbocyanines, see, for example, JP-B-44-32753 and JP-B-46-11627.
And Japanese Patent Publication Nos. Sho 57-1483 and Merocyanine, for example, Japanese Patent Publication Nos. 48-38408, 48-41204, and 50-
No. 40662, JP-A-56-25728, JP-A-58-10753, JP-A-58-9
Nos. 1445, 59-116645 and 50-33828.

As for the combination of thiacarbocyanine with other carbocyanines, for example, JP-B-43-4932,
Nos. 43-4933, 45-26470, 46-18107, 47-
No. 8741, JP-A-59-114533, and JP-B-49-62 using zero methine or dimethine merocyanine, monomethine or trimethine cyanine and a styrene dye.
The method described in No. 07 can be advantageously used.

These sensitizing dyes are added in advance as a dye solution, for example, methyl alcohol, ethyl alcohol, acetone, dimethylformamide, or JP-B-50-40659.
It is used by dissolving it in a hydrophilic organic solvent such as a fluorinated alcohol described in the above item.

The timing of addition may be at any time at the start of chemical ripening of the silver halide emulsion, during ripening, or at the end of ripening. In some cases, it may be added to the step immediately before the emulsion coating.

The photographic constituent layers of a silver halide color photographic light-sensitive material include:
A dye (AI dye) that decolorizes in a water-soluble or color developing solution can be added, and the AI dye includes oxonol dye, hemioxonol dye, merocyanine dye and azo dye. Among them, oxonol dyes, hemioxonol dyes and merocyanine dyes are useful. Examples of AI dyes that can be used include British Patent Nos. 584,609 and 1,2;
No. 77,429, JP-A-48-85130, JP-A-49-99620, JP-A-49-99620
114420, 49-129537, 52-108115, 59-25
No. 845, No. 59-111640, No. 59-111641, U.S. Pat.
74,782, 2,533,472, 2,956,079, 3,125,44
No. 8, No. 3,148,187, No. 3,177,078, No. 3,247,127,
3,260,601, 3,540,887, 3,575,704, 3,6
Nos. 53,905, 3,718,472 and 4,070,352.

These AI dyes are generally used in two moles per mole of silver in the emulsion layer.
It is preferable to use from × 10 ^{-3 to} 5 × 10 ^-1 mol.

Further, in addition to the DIR compound, a compound which releases a development inhibitor upon development can be used in the present invention. For example, U.S. Pat. Nos. 3,297,445 and 3,379,529, West German Patent Application (OLS) 2,417,914, and JP-A-52-914. No. 15271, 53-9116
And Nos. 59-123838 and 59-127038.

The DIR compound 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 a DIR compound is a DIR coupler in which a group capable of forming a compound having a development inhibiting action when released from the active site is introduced into the active site of the coupler, for example, British Patent 935,454. U.S. Patent 3,22
Nos. 7,554, 4,095,984 and 4,149,886.

When the above DIR coupler is subjected to a coupling reaction with an oxidized form of a color developing agent, the coupler nucleus forms a dye,
On the other hand, it has the property of releasing a development inhibitor. In the present invention, U.S. Patent Nos. 3,652,345, 3,928,041, 3,958,99
No. 3, 3,961,959, 4,052,213, JP-A-53-11052
No. 9, 54-13333, and 55-161237, when a coupling reaction with an oxidized form of a color developing agent releases a development inhibitor, but there are also compounds that do not form a dye. included.

Further, when reacted with an oxidized form of a color developing agent as described in JP-A-54-145135, JP-A-56-114946 and JP-A-57-154234, the mother nucleus forms a dye or a colorless compound. On the other hand, a so-called timing DIR compound in which the released timing group releases a development inhibitor by an intramolecular nucleophilic substitution reaction or elimination reaction can also be used in the present invention.

In addition, the timing group as described above is present in a coupler nucleus which forms a completely diffusible dye when reacted with an oxidized form of a color developing agent described in JP-A-58-160954 and JP-A-58-162949. Bound timing DIR compounds can also be used.

The amount of the DIR compound contained in the light-sensitive material is preferably in the range of 1 × 10 ^-4 mol to 10 × 10 ^-1 mol per mol of silver.

90 mol% of silver halide grains used when the color photosensitive material is for positive images (for example, color negative paper)
It has the above-mentioned silver chloride content, and preferably has a silver bromide content of 10 mol% or less and a silver iodide content of 0.5 mol% or less. More preferably, it is silver chlorobromide having a silver bromide content of 0.1 to 2 mol%.

The silver halide grains may be used alone or as a mixture with other silver halide grains having different compositions. Further, it may be used by mixing with silver halide grains having a silver chloride content of 10 mol% or less.

Further, in a silver halide emulsion layer containing silver halide grains having a silver chloride content of 90 mol% or more, the silver chloride content of all silver halide grains contained in the emulsion layer is 90%. The proportion of silver halide grains of at least mol% is 60
% By weight, preferably 80% by weight or more.

The composition of the silver halide grains may be uniform from the inside to the outside of the grains, or the inside and outside compositions of the grains may be different. When the inside and outside compositions of the particles are different, the composition may change continuously or may be discontinuous.

The grain size of the silver halide grains is not particularly limited, but is preferably 0.2 to 1.6 μm, more preferably 0.25 to 1.1, in consideration of other photographic properties such as rapid processing property and sensitivity.
The range is 2 μm.

In addition, the said particle diameter can be measured by various methods generally used in the said technical field. A typical method is Loveland's “particle size analysis method”.
(ASTM Symposium on Right Microscopy, 1955, pp. 94-122) or "Theory of Photographic Processing"
(Mies and James, Third Edition, Chapter 2 of Macmillan, 1966).

The particle size can be measured using the projected area of the particle or the approximate diameter. If the particles are substantially uniform in shape, the particle size distribution can represent this quite accurately as diameter or projected area.

The particle size distribution of the silver halide grains may be polydisperse or monodisperse. Preferably, in the particle size distribution of the silver halide grains, the coefficient of variation is 0.
Monodispersed silver halide grains of 22 or less, more preferably 0.15 or less, are used. Here, the coefficient of variation is a coefficient indicating the breadth of the particle size distribution, and is defined by the following equation.

Here, ri represents the particle size of each particle, and ni represents its number. The particle size referred to here is the diameter of a spherical silver halide grain, or the diameter of a cubic or non-spherical grain when the projected image is converted to a circular image of the peripheral area. .

The silver halide grains used in the above emulsion are prepared by an acid method,
It may be obtained by either the neutral method or the ammonia method. The particles may be grown at one time, or may be grown after seed particles have been made. The method of producing the seed particles and the method of growing may be the same or different.

The method of reacting the soluble silver salt with the soluble halogen salt may be any of a forward mixing method, a reverse mixing method, a simultaneous mixing method and a combination thereof, but a method obtained by the simultaneous mixing method is preferable. Furthermore, as one form of the simultaneous mixing method,
The pAg-controlled double jet method described in 48521 and the like can also be used.

If necessary, a silver halide solvent such as thioether may be used. Further, a compound such as a mercapto group-containing compound, a nitrogen-containing heterocyclic compound or a sensitizing dye may be added at the time of forming silver halide grains or after the completion of grain formation.

Any shape of the silver halide grains can be used. One preferable example is a cube having a {100} plane as a crystal surface. Also U.S. Patent 4,183,75
No. 6, 4,225,666, JP-A-55-26589, JP-B-Showa 55
Octahedral, tetrahedral, dodecahedral, etc. by the method described in -42737 and the literature such as The Journal of Photographic Sunence (J. Photgr. Sci.), 21 , 39 (1973). Particles having a shape can be produced and used. Further, particles having a twin plane may be used. As the silver halide grains according to the present invention, grains having a single shape may be used, or grains having various shapes may be mixed.

The silver halide grains are formed by using a cadmium salt, a zinc salt, a lead salt, a thallium salt, an iridium salt or a complex salt, a rhodium salt or a complex salt, an iron salt or a complex salt in a process of forming and / or growing the grain. Metal ions can be added and included inside and / or on the surface of the particles,
The emulsion containing silver halide grains can provide a reduction sensitizing nucleus inside the grains and / or on the surface of the grains by placing the emulsion in an appropriate reducing atmosphere. The soluble salts may be removed or may remain contained. When removing the salts, use Research Disclosure 1764
The silver halide grains that can be carried out based on the method described in No. 3 may be grains whose latent image is mainly formed on the surface or grains mainly formed inside the grain. Preferably, the latent image is a particle mainly formed on the surface.

 The above emulsion is chemically sensitized by a conventional method.

The arrangement of the respective silver halide emulsion layers of the positive color photographic light-sensitive material is, in order from the support side, a blue-sensitive silver halide emulsion layer containing a yellow coupler, a green photosensitive silver halide emulsion layer containing a magenta coupler, and a cyan coupler. The light-sensitive material as a whole is preferably a blue-sensitive silver halide emulsion layer containing a yellow coupler and a magenta coupler as an essential layer on a support from the support side as an essential layer. A green photosensitive silver halide emulsion layer, a non-photosensitive intermediate layer containing an ultraviolet absorber, a red photosensitive silver halide emulsion layer containing a cyan coupler, a non-photosensitive layer containing an ultraviolet absorber, and a protective layer are arranged. preferable.

As the ultraviolet absorbent, those represented by the following general formula [U-1] are preferable.

(In the above general formula [U], R ₁ , R ₂ and R ₃ each represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group,
Represents an alkoxy group, an aryloxy group, an alkenyl group, a nitro group or a hydroxyl group. Each group represented by R _{1 to} R ₃ includes those having a substituent.

Among the groups represented by R ₁ and R ₂ , a hydrogen atom, an alkyl group, an alkoxy group and an aryl group are preferable, and a hydrogen atom, an alkyl group and an alkoxy group are particularly preferable.

Among the groups represented by R ₃ , a hydrogen atom, a halogen atom, an alkyl group, and an alkoxy group are particularly preferred.

At least one of R _{1 to} R ₃ is preferably an alkyl group, and more preferably at least two are alkyl groups. Further, at least one of R _{1 to} R ₃ is preferably a branched alkyl group.

 A typical example is shown.

The amount of the compound represented by the general formula [U] is preferably 0.1 to 300% by weight, more preferably 1 to 200% by weight, based on the binder of the layer to which the compound is added.

The silver halide color photographic light-sensitive material used in the present invention may further contain various photographic additives. For example, antifoggants, stabilizers, ultraviolet absorbers described in Research Disclosure Magazine No. 17643,
Color stain inhibitors, fluorescent brighteners, color image fading inhibitors, antistatic agents, hardeners, surfactants, plasticizers, wetting agents and the like can be used.

In the silver halide color photographic light-sensitive material used in the present invention, hydrophilic colloids used for preparing emulsions include gelatin, derivative gelatin, graft polymers of gelatin and other polymers, proteins such as albumin and casein. , Hydroxyethyl cellulose derivatives, cellulose derivatives such as carboxymethyl cellulose, starch derivatives, polyvinyl alcohol, polyvinyl imidazole,
An arbitrary one such as a single or copolymer synthetic hydrophilic polymer such as polyacrylamide is included.

Examples of the support of the silver halide color photographic light-sensitive material used in the present invention include, for example, baryta paper, polyethylene-coated paper, polypropylene synthetic paper, a transparent support having a reflective layer, or a combined use of a reflector, for example, a glass plate, Cellulose acetate, cellulose nitrate or polyester film such as polyethylene terephthalate,
Examples thereof include a polyamide film, a polycarbonate film, and a polystyrene film, and other ordinary transparent supports may be used.

These supports are appropriately selected according to the purpose of use of the light-sensitive material.

〔Example〕

Next, the present invention will be described more specifically with reference to examples, but the present invention is not limited thereto.

In Example 1 all examples, the amount of silver halide photographic light-sensitive material is particularly shows the g per 1 m ² unless otherwise noted.
Further, silver halide and colloidal silver are shown in terms of silver.

Samples I of a multilayer color photographic element were prepared by sequentially forming layers having the following compositions on a triacetyl cellulose film support from the support side.

Sample-I First layer: Antihalation layer (HC-1) Black colloidal silver 0.20 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 Second layer: Intermediate layer (LL-1) Ultraviolet absorber (UV-1) ... 0.01 High boiling solvent (Oil-1) ... 0.01 Gelatin ... 1.3 Third layer: Low Sensitivity red-sensitive emulsion layer (RL) Silver iodobromide emulsion (Em-1) 1.0 (Em-2) 0.7 Sensitizing dye (S-1) 2.2 × 10 ^-4 (mol / silver 1 mol) (S-2) 2.5 × 10 ^-4 (〃) 〃 (S-3) 0.5 × 10 ^-4 (〃) Cyan coupler (C'-4) 1.3 (C'-2) 0.15 colored cyan Coupler (CC-1) 0.05 DIR compound (D-1) 0.0015 High boiling solvent (Oil-1) 0.5 Gelatin 1.3 1.3 Fourth layer: Highly sensitive red-sensitive emulsion layer (RH) Silver iodobromide emulsion (E m-3) 2.2 sensitizing dye (S-1) 2.2 × 10 ^-4 (mol / silver 1 mol) 〃 (S-2) 2.0 × 10 ^-4 (〃) sensitizing dye (S-3) 0.1 × 10 ^-4 (mol / silver 1 mol) Cyan coupler (C'-1) 0.15 〃 (C'-2) 0.018 〃 (C'-3) 1.20 Colored cyan coupler (CC-1) 0.015 DIR compound (D-2) ... 0.04 High boiling point solvent (Oil-1) ... 0.5 Gelatin ... 1.3 Fifth layer: Intermediate layer (LL-2) Gelatin ... 0.5 Sixth layer: Low sensitivity green-sensitive emulsion layer (GL) Silver iodobromide emulsion (Em-1) 0.9 Sensitizing dye (S-4) 5 × 10 ^-4 (mol / silver 1 mol) 〃 (S-5) 1 × 10 ^-4 (〃) Magenta coupler (M'-1) ... 0.5 Colored magenta coupler (CM-1) ... 0.05 DIR compound (D-3) ... 0.015 〃 (D-4) ... 0.020 High boiling solvent (Oil-2) ... 0.5 Gelatin ... 1.2 Layer: Middle layer (IL-3) ... 0.7 High boiling solvent (Oil-1) ... 0.2 8th layer: high sensitivity green-sensitive emulsion layer (GH) Silver iodobromide emulsion (Em-3) ... 1.2 Sensitizing dye (S-6) ... 1.5 × 10 - ⁴ (mol / silver 1 mol) 〃 (S-7): 2.5 × 10 ^-4 (〃) 〃 (S-8): 0.7 × 10 ^-4 (〃) Magenta coupler (M'-2): 0.08〃 ( M'-3) 0.18 Colored magenta coupler (CM-2) 0.05 DIR compound (D-3) 0.01 High boiling solvent (Oil-3) 0.5 Gelatin 1.15 Ninth layer: yellow filter layer (YC) Yellow Colloidal silver 0.10 Color stain inhibitor (SC-1) 0.1 High-boiling point solvent (Oil-3) 0.1 Gelatin 0.9 0.9 Layer 10: Low-sensitivity blue-sensitive emulsion layer (BL) Silver iodobromide emulsion (Em-1) ) 0.233 (Em-2) 0.27 Sensitizing dye (S-10) 7 × 10 ^-4 (mol / silver 1mol) Yellow coupler (YB-15) 0.6 〃 (Y-2) 0.12 DIR Compound (D-2) ... 0.0 1 High boiling point solvent (Oil-3) ... 0.15 Gelatin ... 1.0 11th layer: High-sensitivity blue-sensitive emulsion layer (BH) Silver iodobromide emulsion (Em-4) ... 0.45E (Em-1) ... 0.22 Sensitizing dye (S-9) 1.3 x 10 ^-4 (mol / silver 1 mol) 〃 (S-10) 3 x 10 ^-4 (〃) Yellow coupler (YB-15) 0.36 〃 (Y-2) 0.09 High boiling point solvent (Oil-3) ... 0.07 Gelatin ... 1.1 12th layer: 1st protective layer (PRO-1) Fine grain silver iodobromide emulsion ... 0.25 (average particle size 0.06 µm AgI 2.0 mol%) UV absorber (UV -1)… 0.10UV (UV-2)… 0.05 High boiling solvent (Oil-1)… 0.1 il (Oil-4)… 0.1 Formalin scavenger (HS-1)… 0.5 〃 (HS-2)… 0.2 Gelatin… 1.0 13th layer: 2nd protective layer (PRO-2) Surfactant (Su-1) ... 0.005 Alkali-soluble matting agent ... 0.10 (average particle size 2 m) Cyan dye (AIC-1) ... 0.005 Magenta dye ( AIM-1) ... 0.01 Sliding agent (WAX-1) ... 0.04 Gelatin ... 0.6 In addition to the above composition, each layer has a coating aid Su-2, a dispersion aid Su-3, a preservative DI-1, Stabilizer Stab-1 and antifoggants AF-1 and AF-2 were added.

Em-1 Average grain size 0.45 μm, average silver iodide content 7.5 mol% Monodisperse surface low silver iodide content emulsion Em-2 Average grain size 0.30 μm, average silver iodide content 2.1 mol% monodispersion Emulsions having uniform composition Em-3 average grain size 0.81 μm, average silver iodide content 6.1 mol% monodisperse surface-low silver iodide-containing emulsion Em-4 average grain size 0.98 μm, average silver iodide content 8.0 mol% monodisperse surface-low silver iodide-containing emulsions Em-1, Em-3 and Em-4 are disclosed in JP-A-60-138538.
It is a silver iodobromide emulsion having a multilayer structure adjusted with reference to each publication of JP-A No. 61-245151 and mainly comprising an octahedron. Also
Regardless of Em-1 to Em-4, the average value of particle size / particle thickness is
1.0, and the size distribution of the particles is 12,8,12 and 12, respectively.
10%.

The thus-prepared sample was exposed to wedges using white light, and then subjected to the following development processing.

<Experimental processing> Processing step Processing time Processing temperature Color development (1 tank) 3 minutes 15 seconds 38 ° C Bleaching (〃) 35 seconds 38 ° C Settling (1) 1 minute 10 seconds 38 ° C Stabilization (3 tank cascade) 1 minute 38 ° C drying (40 ° C to 80 ° C) 1 minute The composition of the color developing solution used is as follows.

Potassium carbonate 30 g Sodium bicarbonate 2.5 g Potassium sulfite 3.0 g Sodium bromide 1.3 g Potassium iodide 1.2 mg Hydroxylamine sulfate 2.5 g Sodium chloride 0.6 g 4-Amino-3-methyl-N-ethyl-N- (β-hydroxyl Ethyl) Aniline sulfate 4.5 g Diethylenetriaminepentaacetic acid 3.0 g Potassium hydroxide 1.2 g Add water to make 1 and adjust to pH 10.06 with potassium hydroxide or 20% sulfuric acid.

 The composition of the bleaching solution used is as follows.

Ferric organic acid sodium salt (described in Table 1) Disodium ethylenediaminetetraacetate 10 g Potassium bromide 150 g Glacial acetic acid 40 ml The above color developing solution 250 ml Water was added to adjust the pH to 1 using diethanolamine, aqueous ammonia or glacial acetic acid. It was adjusted appropriately as shown in Table 1, and the ratio of ammonium salt to all cations was adjusted to 5%.

 The composition of the fixing solution used is as follows.

Ammonium thiosulfate 250 g Anhydrous sodium bisulfite 12 g Sodium metabisulfite 2.5 g Disodium ethylenediaminetetraacetate 0.5 g The above-mentioned bleaching solution 100 ml Water was added to adjust the pH to 1 using acetic acid and ammonia water.
Adjust to 5.

 The composition of the stabilizer used was as follows.

Formaldehyde (37% solution) 0.5 ml 5-chloro-2-methyl-4-isothiazolin-3-one 0.05 g Emulgen 810 1 ml hexahydro-1,3,5-tris- (2-hydroxyethyl) -5-triazine 0.3 g Sodium formaldehyde bisulfite adduct 2g Hexamethylenetetramine 0.2g Add water to make 1 and adjust the pH with ammonia water and 50% sulfuric acid.
Adjusted to 7.0.

As shown in Table 1 below, the ferric complex salt of the organic acid in the bleaching solution, the amount thereof added, and the pH were changed, and the resulting solution was stored at 38 ° C. for 1 week, and then subjected to development processing, and the unexposed portion of the processed film sample was processed. Was measured at the same time, and the amount of residual silver in the exposed portion was measured by a fluorescent X-ray method. Further, the appearance of the bleaching solution after storage was observed to check the state of tar generation. The above results are summarized in Table 1.

In the table, EDTA • Fe is ferric sodium salt of ethylenediaminetetraacetic acid, NTA • Fe is sodium ferric nitrilotriacetic acid salt, CyDTA • Fe is sodium ferric salt of 1,2-cyclohexanediaminetetraacetic acid, EDTMP • Fe Is ferric ethylenediaminetetramethylenephosphonic acid sodium salt, NTMP • Fe is ferric nitrilotrimethylenephosphonic acid sodium salt,
(A-1) · Fe means ferric sodium salt of (A-1). (A-4) -Fe, (A-7) -Fe and (A-
9) Fe also means ferric sodium salt of (A-4), (A-7) and (A-9), respectively.

Further, in the table, ○ means that no tar is generated, △ means that there is some generation, X means that generation of tar is clearly recognized, and the larger the number of ×, the more remarkable.

According to Table 1, the organic acid ferric complex is a ferric complex of the compound represented by the general formula [A] of the present invention, the amount of which is 0.10 mol / l or more, and the pH is 2.0 to 2.0 mol / l. At 5.5, the yellow fog density in the unexposed area was low, the amount of residual silver was very small, no tar was generated in the bleaching solution, and both performances were good. However, when any one of the three items deviates from the conditions, any one of the performances is inferior and cannot be put to practical use.

Example 2 The same evaluation as in Example 1 was performed for Example Nos. 1-1, 1-6, and 1-8 except that the ratio of ammonium salt to all cations was changed as shown in Table 2.

However, the ratio of the ammonium salt was adjusted by changing the ratio of the ammonium salt and the sodium salt of the ferric complex salt or by adding aqueous ammonia.

 The results are shown in Table 2.

As is clear from Table 2, when the ratio of the ammonium salt to the total cation is high, the ferric complex salt of the present invention shows that EDTA · Fe
Marked increase in yellow stain compared to
At 60% or more, the yellow stain is high. or,
It can be seen that when the ratio of ammonium salt is high, the desilvering property of EDTA.Fe is relatively good, but in the case of the ferric complex salt of the present invention, it is not so remarkable.

Example 3 Silver iodobromide emulsions (Em-1 to 3, 4, 6, 8, 10, 11 and 12 layers) of the silver halide color photographic light-sensitive material used in Example 1
4 and a fine grain silver iodobromide emulsion) were processed in the following processing steps and processing solution using the same photosensitive material except that the silver chlorobromide emulsion shown in the following table was used. went.

The above emulsion was prepared with reference to JP-A-64-26838 and JP-A-64-26837.

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

Triethanolamine 10 g Ethylene glycol 1 g N, N-diethylhydroxylamine 3.6 g Hydrazinodiacetic acid 5.0 g Potassium bromide 20 mg Potassium chloride 2.5 g Diethylenetriaminepentaacetic acid 5 g Potassium sulfite 5.0 × 10 ^-4 mol Color developing agent (3-methyl-4- Amino-N-ethyl-N- (β-methanesulfonamidoethyl) -aniline sulfate) 5.5 g Potassium carbonate 25 g Potassium hydrogen carbonate 5 g Add water to make the total volume 1 and adjust to pH 10.10 with potassium hydroxide or sulfuric acid. I do.

The same bleaching solution, fixing solution and stabilizing solution as in Example 1 were used.

As a result, substantially the same effects as in Example 2 could be obtained.

Example 4 The silver halide color photographic light-sensitive material used in Example 2 was changed to the following color photographic light-sensitive material, and the processing steps and processing solutions were changed as follows.

Sample-II Each layer having the following composition was coated on a support obtained by laminating polyethylene on one side of a paper support and polyethylene containing titanium oxide on the first layer side of the other side, and forming a multilayer silver halide color. Photographic material (1) was prepared. The coating solution was adjusted as described below.

First layer coating solution 26.7 g of yellow coupler (Y-1), 10.0 g of dye image stabilizer (ST-1), 6.67 g of (ST-2), additive (HQ-
1) 0.67 g of ethyl acetate 6 in 6.67 g of high boiling organic solvent (DNP)
0 ml was added and dissolved, and this solution was added to a 20% surfactant (SU-
1) A yellow coupler dispersion was prepared by emulsifying and dispersing in 220 ml of a 10% aqueous gelatin solution containing 7 ml using an ultrasonic homogenizer. This dispersion was mixed with a blue-sensitive silver halide emulsion (containing 10 g of silver) prepared under the following conditions to prepare a first layer coating solution.

The coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer.

In addition, the following H-1 was used as a hardener.

[Preparation Method of Blue-Sensitive Silver Halide Emulsion] The following (solution A) and (solution B) were adjusted to pAg = 6.5 and pH = 3.0 in 1000 ml of a 2% aqueous gelatin solution kept at 40 ° C.
Simultaneous addition over 30 minutes, and the following (Solution C) and (Solution D)
Was added simultaneously over 180 minutes while controlling pAg = 7.3 and pH = 5.5.

At this time, pAg was controlled by the method described in JP-A-59-45437, and pH was controlled using an aqueous solution of sulfuric acid or sodium hydroxide.

(Solution A) Sodium chloride 3.42 g Potassium bromide 0.03 g Add water 200 ml (Solution B) Nitric acid solution 10 g Add water 200 ml (Solution C) Sodium chloride 102.7 g Potassium bromide 1.0 g Add water 600 ml (D Liquid) 300 g of silver nitrate, 600 ml of water was added, and after the addition was completed, desalting was carried out using a 5% aqueous solution of Demol N and 20% aqueous solution of magnesium sulfate manufactured by Kao Atlas Co., Ltd. A monodispersed cubic emulsion EMP-1 having a thickness of 9 μm, a coefficient of variation (σ / r) of 0.07 and a silver chloride content of 99.5 mol% was obtained.

To the above emulsion EMP-1, 9
Chemical ripening was performed for 0 minutes to obtain a blue-sensitive silver halide emulsion (EmA).

Sodium thiosulfate 0.8 mg / mol AgX chloroauric acid 0.5 mg / mol AgX stabilizer SB-5 6 × 10 ^-4 mol / mol AgX sensitizing dye D-1 4.3 × 10 ^-4 mol / mol AgX D-4 0.7 × 10 ^-4 mol / mol AgX [Preparation method of green-sensitive silver halide emulsion] Addition time of (solution A) and (solution B), and (D) and (D)
EMP-2), except that the addition time of the liquid was changed, a monodisperse cubic emulsion EMP-2 having an average particle size of 0.43 μm, a coefficient of variation (σ / r) = 0.08, and a silver chloride content of 99.5 mol% was prepared. Obtained.

EMP-2 was chemically ripened at 55 ° C. for 120 minutes using the following compound to obtain a green-sensitive silver halide emulsion (EmB).

Sodium thiosulfate 1.5 mg / mol AgX chloroauric acid 1.0 mg / mol AgX stabilizer SB-5 6 × 10 ^-4 mol / mol AgX sensitizing dye D-2 4 × 10 ^-4 mol / mol AgX [red-sensitive halogenation Preparation method of silver emulsion] (solution A) and (solution B) addition time and (solution C) and (D
EMP-3 in the same manner as in EMP-1 except that the addition time of the solution was changed. A monodispersed cubic emulsion EMP-3 having an average particle size of 0.50 μm, a coefficient of variation (σ / r) = 0.08, and a silver chloride content of 99.5 mol% was obtained. Obtained.

EMP-3 was chemically ripened at 60 ° C. for 90 minutes using the following compounds to obtain a red-sensitive silver halide emulsion (EmC).

Sodium thiosulfate 1.8 mg / mol AgX chloroauric acid 2.0 mg / mol AgX stabilizer SB-5 6 × 10 ^-4 mol / mol AgX sensitizing dye D-3 1.0 × 10 ^-4 mol / mol AgX After exposing this sample according to a conventional method, the same evaluation as in Example 2 was performed using the following processing step and processing solution.

(Color developing tank solution) Same as the color developing solution of Example 3.

(Bleaching and fixing) Same as in Example 1.

(Stabilizing Solution) ortho-phenyl phenol 0.1g Uvitex (Ciba _{Geigy) 0.5g ZnSO 4 · 7H 2 O} 0.15g Ammonium sulfite (40% solution) 4.5 ml 1-hydroxyethylidene--1,1-2.0 g diphosphonic acid (60 % Solution) Ethylenediaminetetraacetic acid 1.0g Adjust the pH to 7.5 with aqueous ammonia or sulfuric acid and add 1% with water.
And

As a result, almost the same results as in Example 2 were obtained,
Although the degree of stain was slightly more likely to occur as compared with the silver halide color photographic light-sensitive material of Example 1, it could be effectively prevented by reducing the ratio of ammonium salt to all cations as described above.

Example 5 The color developing agent of the color developing solution of Example 1 was changed to 3-methyl-
Example 1 except that 4-amino-N-ethyl-N- (β-methanesulfonamidoethyl) -aniline sulfate was used.
The same evaluation was performed.

 The results are shown in Table 3.

As is apparent from the results in Table 3, the color developing agent was 4-amino-3-methyl-N-ethyl-N- (β-hydroxylethyl) aniline sulfate (hereinafter referred to as CD-4) and 3-methyl-4- By changing to amino-N-ethyl-N- (β-methanesulfamidoethyl) aniline sulfate (hereinafter referred to as CD-3), the tendency of yellow stain generation is not changed much, but by changing to CD-3, bleaching is achieved. The fog is slightly lower, which is a preferred embodiment of the present invention.

Example 6 Using the color photographic material used in Example 1, a running process was performed with the following processing solution.

<Color developer> The color developer used in Example 1.

<Color developing replenisher> Potassium carbonate 35 g Sodium hydrogen carbonate 3 g Potassium sulfite 5 g Sodium bromide 0.5 g Hydroxylamine sulfate 3.1 g 4-Amino-3-methyl-N-ethyl-N- (β-hydroxyethyl) aniline sulfate 5.8 g Potassium hydroxide 2 g Diethylenetriaminepentaacetic acid 1.5 g Add water to make 1 and adjust to pH 10.12 with potassium hydroxide or 20% sulfuric acid.

<Bleaching solution> Organic acid ferric potassium salt 0.3 mol (described in Table 4) Ethylenediaminetetra 5.0 g Disodium acetate Potassium bromide 150 g Glacial acetic acid 40 ml Potassium nitrate 30 g Water was added to make 1 to 1 based on all cations described in Table 4 Adjust to the ratio of ammonium salt and adjust the pH to 4.2
And

 The composition of the bleaching replenisher used was as follows.

Organic acid ferric potassium salt 0.32 mol Ethylenediaminetetraacetic acid disodium 2 g Potassium bromide 178 g Glacial acetic acid 50 ml Potassium nitrate 30 g Water was added to 1 so that the ratio of ammonium salt to all cations shown in Table 4 was adjusted to pH 3. Adjust to 5.

 The composition of the fixing solution used is as follows.

Sodium thiosulfate 100 g Potassium thiocyanate 150 g Anhydrous sodium bisulfite 12 g Sodium metabisulfite 2.5 g Ethylenediaminetetraacetic acid 0.5 g Disodium Add water to make 1 and add with diethanolamine or acetic acid
The pH was adjusted to 6.5.

 The composition of the fixing replenisher used was as follows.

Potassium thiosulfate 130 g Potassium thiocyanate 190 g Anhydrous sodium bisulfite 15 g Sodium metabisulfite 3 g Disodium ethylenediaminetetraacetic acid 0.8 g Add water to make 1. The pH was adjusted to 6.5.

 As the stabilizing replenisher, the stabilizing solution of Example 1 was used.

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

The running process was performed until the bleach replenisher was replenished in an amount twice the bleach tank capacity. After the running process, the yellow density in the unexposed area and the residual silver amount in the highest density area were measured.

 The results are summarized in Table 4.

As is apparent from Table 4, bleaching fog is effectively prevented by reducing the ratio of ammonium salt to all cations even in the running treatment.

Example 7 Same as Example 6 except that the replenishment amount of the bleaching solution was changed as shown in Table 5 using Experiment Nos. 4-1 and 4-5 and 4-6 and 4-10 of Example 6. Was evaluated.

 The results are shown in Table 5.

As is clear from Table 5, when the replenishment amount of the bleaching solution is reduced, yellow stain is likely to be generated. However, when the bleaching solution of the present invention is used, the increase in bleaching fog is prevented regardless of the replenishment amount. It can be seen that the effect of the present invention becomes remarkable when the replenishment amount of the bleaching solution is reduced.

Example 8 The same evaluation as in Example 7 was performed using the color paper of Example 4 and the following processing steps and processing solutions.

<Treatment process> Same as the treatment process of the fourth embodiment.

<Color developing tank solution> Triethanolamine 10 g Ethylene glycol 6 g Tinopearl SFP (Ciba-Geigy) 1 g Ubitex MST (Ciba-Geigy) 1 g N, N-diethylhydroxylamine 3.6 g Potassium bromide 20 mg Potassium chloride 2.5 g Diethylenetriaminepentaacetic acid 5 g Potassium sulfite 5.0 × 10 ^-4 mol Color developing agent (3-methyl-4-amino-N-ethyl-
N- (β-methanesulfonamidoethyl) -aniline sulfate) 5.5 g Potassium carbonate 25 g Potassium hydrogen carbonate 5 g Add water to make the total amount 1, and adjust to pH 10.10 with potassium hydroxide or sulfuric acid.

<Color developing replenisher> Triethanolamine 14.0 g Ethylene glycol 8.0 g Tinopearl SFP (Ciba-Geigy) 1.2 g Ubitex MST (Ciba-Geigy) 1.5 g N, N-diethylhydroxylamine 5 g Potassium bromide 8 mg Potassium chloride 0.3 g Diethylenetriaminepentaacetic acid 7.5 g Potassium sulfite 7.0 × 10 ^-4 mol Color developing agent (3-methyl-4-amino-N-ethyl-
N- (β-methanesulfonamidoethyl) -aniline sulfate 8 g Potassium carbonate 30 g Potassium hydrogen carbonate 1 g Add water to make the total volume 1 and adjust to pH 10.40 with potassium hydroxide or sulfuric acid.

<Bleaching solution and replenishing solution for bleaching> Ferric organic acid potassium salt 0.15 mol Disodium ethylenediaminetetraacetate 1.0 g Potassium bromide 50 g Glacial acetic acid 20 ml Potassium nitrate 30 g Water was added to 1 to adjust the pH to 4.5.

<Fixing Solution and Fixing Replenisher> Potassium thiosulfate 70 g Potassium thiocyanate 20 g Sodium sulfite 15 g Disodium ethylenediaminetetraacetate 0.5 g Water was added to 1 to adjust the pH to 6.0.

The replenishment rate of <stabilizing solution and stabilizing replenisher> Example 4 stabilizer each processing solution described color photographic materials 1 m ² per color developer 60 ml / m ^2, the bleaching solution 30 ml / m ^2, the fixing solution 60 ml / m ² and The stable liquid was 250 ml / m ² , and the same evaluation as in Example 7 was performed.

Example 9 In Example 6, the bleaching tank and the fixing tank had a diameter of 0.
A 5-mm-drilled vinyl chloride nozzle was installed, and a processing solution was sprayed onto the emulsion surface of the photosensitive material using an Iwaki magnet pump MD-15. Further, the crossover time between the color developing tank and the bleaching tank was 8 to 5 seconds. The experiment was performed in the same manner except for the above. As a result, the unexposed area yellow density is further 0.01 to 0.02.
The residual silver content was reduced by half.

Example 10 Using a sample in which the yellow coupler Y-2 in Sample I and the yellow coupler Y-1-3 in Sample II were each replaced with an equimolar yellow coupler shown in Table 6, each of Example 6 or Example The treatment was carried out using the treatment liquid of the treatment step of Example 8, and the yellow density of the unexposed portion was measured.

However, the bleaching agent of the bleaching solution used was (A-1) .Fe, in which the ratio of ammonium was 0, and a treatment solution whose pH was adjusted using triethanolamino or acetic acid was used. Sample I was measured by transmission density, and sample II was measured by reflection density.

 The results are shown in Table 6.

As is clear from Table 6, the bleaching fog was improved by about 0.01 to 0.03 by changing the yellow stain in the unexposed portions of Samples I and II to a preferable yellow coupler for practicing the present invention.

However, when the YR-1 coupler was used in Sample II, the yellow density was 0.08.

In addition, the above effects were also observed for YB-21, YB-22, YB-23 and YB-32.

Example 11 Magenta Couplers M'-2 and M'- in Sample I
3. Magenta coupler M-1 in Sample II was replaced with the same magenta coupler as shown in Table 7 by using only the same amount of magenta coupler as described in Table 7, and the magenta coupler M-1 was treated with the treatment steps and treatment solutions of Example 6 or Example 8, respectively. The magenta density of the exposed part was measured. The bleaching solution used had the composition described in Example 10.

 The results are shown in Table 7.

As is clear from Table 7, in Samples I and II, the magenta stain in the unexposed portion was improved by changing to a preferable magenta coupler for practicing the present invention.

Further, in addition to the magenta couplers shown in Table 7, M-20, 21,
31, 46, 76, 78 and 81 were also examined, but almost the same results as in Table 7 were obtained.

Example 12 Samples obtained by changing the cyan couplers C'-2 and C'-3 in Sample I and the cyan coupler C-2-2 in Sample II to the cyan couplers shown in Table 8 in the same molar amount were used. 6 or the processing step of Example 8, the processing was performed with the processing solution, and the cyan density of the unexposed portion was measured. The bleaching solution used had the composition described in Example 10.

 The results are shown in Table 8.

As is clear from Table 8, the use of a cyan coupler which is preferable in practicing the present invention shows a slight improvement in cyan stain.

Example 13 A bleaching solution, a fixing solution, and a stabilizing solution other than the color developing solution used in Example 6 were poured into a tank for color paper processing in Example 8 by flowing an overflow solution during the running process in Example 6.
Continuous processing with replenished pears. As a result, the stain in the color paper was about 0.01 higher than in the case of replenishing without co-injection of Y, M, and C, but the amount of waste liquid was reduced to about 1/2, which is a favorable embodiment with low pollution.

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int.Cl. ⁶ , DB name) G03C 7/42

Claims (3)

(57) [Claims] 1. A method for processing a silver halide color photographic light-sensitive material, comprising treating a silver halide color photographic light-sensitive material with a color developer after imagewise exposure, and immediately thereafter processing with a bleaching solution. Is 50 of all cations
Mol% or less, and the bleaching solution contains at least 0.10 mol / l of a ferric complex salt of a compound represented by the following general formula [A], and the replenishment amount of the bleaching solution is a silver halide color photographic light-sensitive material. A processing method for a silver halide color photographic light-sensitive material, wherein the amount is ^{20 to} 400 ml per 1 m ² . Wherein A _{1 to} A ₄ may be the same or different,
CH ₂ OH, represents a -COOM or -PO ₃ M ₁ M _2. M, M ₁ and M ₂ each represent a hydrogen atom, sodium, potassium or ammonium. X represents a substituted or unsubstituted alkylene group having 3 to 6 carbon atoms. ] 2. The method for processing a silver halide color photographic light-sensitive material according to claim 1, wherein said bleaching solution has a pH of 2.0 to 5.5. 3. A method for processing a silver halide color photographic light-sensitive material according to claim 1, wherein said bleaching solution has an ammonium ion content of not more than 20 mol% of all cations.