JPH07109495B2 - Processing method of silver halide color photographic light-sensitive material - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for processing a silver halide color photographic light-sensitive material, and in particular, the desilvering property is remarkably improved in spite of rapid processing and the dye is leuco-formed. The present invention relates to a treatment method in which is significantly prevented. At the same time, it relates to a treatment method in which color contamination is prevented.

(Prior Art) A color developing solution containing an aromatic primary amine color developing agent has been used for a long time in the formation of color development, and now plays a central role in the image forming method of color photography. Is playing. However, the color developer has a problem that it is very easily oxidized by air or metal, and when a color image is formed using the oxidized developer, fog is increased, sensitivity and gradation are changed. Therefore, it is well known that desired photographic characteristics cannot be obtained.

In particular, with the recent reduction in processing time, the change in photographic characteristics during continuous processing tends to increase, and in some cases, a serious problem of color contamination may occur. Especially, when the desilvering process, the water washing process and the like are shortened, such a problem is likely to occur.

There are many possible causes for such changes in photographic characteristics and color contamination during continuous processing.

For example, A: the color developing solution deteriorates with time, the photographic characteristics fluctuate, and the main agent oxide adheres to the light-sensitive material to cause color contamination.

B; Color developing agent is brought into the bleaching solution or bleach-fixing solution,
Oxidation causes fog and contamination C; Light-sensitive material eluate accumulates in the color developer and adheres to cause color contamination.

D; The dye or sensitizing dye contained in the photosensitive material was insufficiently washed out, and the photosensitive material was colored.

E: The bleach-fix solution and the subsequent rinse solution deteriorate with time, causing color contamination.

Etc.

In particular, in order to solve the problems of A and B, it is a necessary condition to improve the stability of the color developing solution. Sulfite ions have been well known as a preservative for improving the stability of color developers, and it is known that the inclusion of various sulfites in color developers is effective in preventing color contamination. . On the other hand, it was also true that such a sulfite ion has a characteristic that it is unfavorable in terms of photographic characteristics because it lowers the color developability and dissolves a silver halide.

On the other hand, in recent years, in the industry, the speedup of processing,
There is a strong demand for shortening the processing time, and in particular, shortening the desilvering process, which occupies almost half of the processing time, is a major issue.

Conventionally, as a means to accelerate the desilvering process, the German patent No. 1
A bleach-fixing solution containing a ferric aminopolycarboxylic acid complex salt and a thiosulfate described in Japanese Patent No. 866,605 is known, but originally has a weak oxidizing power (bleaching power). Since the ferric aminopolycarboxylic acid complex salt is allowed to coexist with the thiosulfate salt having a reducing power, its bleaching power is significantly weakened, and it is extremely difficult to sufficiently desilver the color light-sensitive material and it cannot be put to practical use. There was a drawback.

Therefore, as a method of increasing the bleaching power, a method of adding various bleaching accelerators to a bleaching bath, a bleaching stabilizing bath or a prebath thereof has been proposed. Examples of such a bleaching accelerator include ammonium bromide described in JP-A-51-87036, water-soluble iodide salts described in British Patent No. 926,569, and JP-B-53-
The halide salts and the like described in No. 11854 are known.

Furthermore, in a bleach-fixing solution using an aminopolycarboxylic acid metal complex salt such as EDTA iron complex salt, when the bleach-fixing process is performed immediately after the step of containing a reducing agent such as a color developing solution, the reducing agent is changed depending on the light-sensitive material. The aminopolycarboxylic acid metal complex salt is reduced by the reducing agent in the bleach-fixing bath or the reducing agent in the bleach-fixing solution, and the reduced form of this aminopolycarboxylic acid metal complex salt reduces the coloring dye, particularly the cyan dye, to form leuco. As a result, there is a problem that so-called color restoration failure occurs, and it is desired to solve this problem.

On the other hand, as cyan couplers for suppressing fading, couplers such as those described in JP-B-49-11572, JP-A-59-166956 and the like are known. Includes what is expected.

(Problems to be Solved by the Invention) However, even if each of the above-mentioned techniques is used alone, the problems of color contamination, desilvering property or color reversion property can be solved to some extent, but still a sufficient effect is obtained. Has not been obtained.

Therefore, it is an object of the present invention to provide a processing method of a silver halide color photographic light-sensitive material, which is remarkably improved in color stain, desilvering property and color-restoring property.

(Means for Solving the Problems) The above object of the present invention is to provide a processing method in which a silver halide color photographic light-sensitive material is exposed and then treated with a color developing solution, and subsequently with a bleach-fixing solution. The solution is substantially free of sulfite ions, and the bleach-fix solution contains 1 × 10 ^-2 to 2 mol of bromide ion and / or 5 per mol.
It is characterized by containing x10 ^{-4 to} 5x10 ^-2 mol of iodide ion, and the color photographic light-sensitive material contains at least one cyan coupler represented by the following general formula (C). It has been found to be achieved by the processing method of silver halide color photographic light-sensitive materials.

General formula (C) (In the formula, R _a represents an alkyl group, a cycloalkyl group, an aryl group, an amino group or a heterocyclic group. R _b represents an acylamino group or an alkyl group having 2 or more carbon atoms. R _c represents a hydrogen atom or a halogen atom. Represents an alkyl group or an alkoxy group, and R _c may combine with R _b to form a ring.
Z _a represents a hydrogen atom, a halogen atom, or a group capable of splitting off upon reaction with an oxidized product of an aromatic primary amine color developing agent. It has been found that, based on the present invention, remarkably excellent effects can be obtained in each of desilvering property, color stain and color recovery property.

The general formula (C) will be described in detail below.

Details of the general formula (I) will be described below.

General formula (C) (In the formula, R _a represents an alkyl group, a cycloalkyl group, an aryl group, an amino group or a heterocyclic group. R _b represents an acylamino group or an alkyl group having 2 or more carbon atoms. R _c represents a hydrogen atom or a halogen atom. Represents an alkyl group or an alkoxy group, and R _c may combine with R _b to form a ring.
Z _a represents a hydrogen atom, a halogen atom, or a group capable of splitting off upon reaction with an oxidized product of an aromatic primary amine color developing agent. In the general formula (C), the alkyl group represented by R _a is preferably an alkyl group having 1 to 32 carbon atoms, such as a methyl group,
A butyl group, a tridecyl group, a cyclohexyl group, an allyl group and the like can be mentioned, an aryl group can be, for example, a phenyl group and a naphthyl group, and a heterocyclic group can be, for example, a 2-pyridyl group and a 2-furyl group. Can be mentioned.

When R _a is an amino group, a phenyl-substituted amino group which may have a substituent is particularly preferable.

R _a is further an alkyl group, an aryl group, an alkyl or aryloxy group (for example, a methoxy group, a dodecyloxy group, a methoxyethoxy group, a phenyloxy group, 2,4-
Di-tert-amylphenoxy group, 3-tert-butyl-4
-Hydroxyphenyloxy group, naphthyloxy group etc.), carboxy group, alkyl or arylcarbonyl group (eg acetyl group, tetradecanoyl group, benzoyl group etc.), alkyl or aryloxycarbonyl group (eg methoxycarbonyl group, phenoxy group) Carbonyl group etc.), acyloxy group (eg acetyl group, benzoyloxy group etc.), sulfamoyl group (eg N-ethylsulfamoyl group, N-octadecylsulfamoyl group etc.), carbamoyl group (eg N
-Ethylcarbamoyl group, N-methyl-dodecylcarbamoyl group, etc.), sulfonamide group (e.g., methanesulfonamide group, benzenesulfonamide group, etc.), acylamino group (e.g., acetylamino group, benzamide group, ethoxycarbonylamino group, A phenylaminocarbonylamino group, etc.), an imide group (eg, succinimide group, hydantoinyl group, etc.), a sulfonyl group (eg, methanesulfonyl group, etc.), a hydroxy group, a cyano group, a nitro group, and a substituent selected from a halogen atom. It may be substituted.

In formula (C), Z _a represents a hydrogen atom or a coupling-off group, and examples thereof include a halogen atom (eg, fluorine atom, chlorine atom, bromine atom, etc.), an alkoxy group (eg, dodecyloxy group). , Methoxycarbamoylmethoxy group, carboxypropyloxy group, methylsulfonylethoxy group, etc.), aryloxy group (eg, 4-chlorophenoxy group, 4-methoxyphenoxy group, etc.), acyloxy group (eg, acetoxy group, tetradecanoyloxy group) Group, benzoyloxy group, etc.), sulfonyloxy group (eg, methanesulfonyloxy group, toluenesulfonyloxy group, etc.), amide group (eg, dichloroacetylamino group, methanesulfonylamino group, toluenesulfonylamino group, etc.), alkoxycarbonyl Oh Si group (eg, ethoxycarbonyloxy group, benzyloxycarbonyloxy group, etc.), aryloxycarbonyloxy group (eg, phenoxycarbonyloxy group, etc.), aliphatic or aromatic thio group (eg, phenylthio group, tetrazolylthio group, etc.) , An imide group (for example, a succinimide group, a hydantoinyl group, etc.), an N-hydrogen ring (for example, a 1-pyrazolyl group, a 1-benztriazolyl group, etc.), an aromatic azo group (for example, a phenylazo group, etc.), etc. is there. These leaving groups may include photographically useful groups.

R _a or R _b in the general formula (C) may form a dimer or a multimer or more.

Specific examples of the cyan coupler represented by the general formula (C) are shown below, but the present invention is not limited thereto.

The cyan coupler represented by the above general formula (C) can be synthesized based on the description in JP-A-59-166956 and JP-B-49-11572.

The content of the present cyan coupler is not particularly limited, but it is preferably 1 × 10 ⁻⁶ to 1 × 10 ⁻² mol, and more preferably 1 × 10 ⁻⁵ to 1 × 10 ⁻³ mol per 1 m ² of the light-sensitive material. .

The bromide ion and iodide ion used in the bleach-fixing solution of the present invention are preferably added to the bleach-fixing solution in the form of a water-soluble bromide salt or iodide salt, and specific compounds include ammonium bromide and Examples thereof include sodium bromide, potassium bromide, ammonium iodide, sodium iodide and potassium iodide, and alkali metal salts, ammonium salts, alkaline earth metal salts and the like of the ions.

The concentration of the bromide ion is between 1 × 10 ^-2 and 2 mol / l,
The concentration of iodide ions is 5 × 10 ^-4 to 5 × 10 ^-2 mol / l
The preferred effects are as follows. Particularly, for bromide ion, 1 × 10 ^-2 to 5 × 10 ^-1 mol is preferable, and for iodide ion, 5 × 10 ^-4 to 1 × 10 ^-2.
It is preferably molar.

Here, the bromide ion concentration is 1 × 10 1 per bleach-fixing solution.
^If it is less than ^-2 mol, the bleach-fixing promoting effect is not exhibited and it is not preferable from the viewpoint of reducing the amount of residual silver which is the object of the present invention. If it exceeds 2 mol, fixing failure occurs, so that it is preferable from the viewpoint of desilvering failure. Absent.

Further, as in the case where the iodide ion concentration is less than 5 × 10 ⁻⁴ mol and the bromide ion concentration is 1 × 10 ⁻² mol or less, it is not preferable from the viewpoint of reducing the residual silver amount, and exceeds 5 × 10 ⁻² mol. Similarly to the case where the bromide ion concentration is 2 mol or more, it is not preferable from the viewpoint of desilvering failure.

When bromide ion and iodide ion are used in combination, the bromide ion can be contained in an amount of 1 × 10 ⁻² to 2 mol per bleach-fixing solution, and iodide ion is 5 ×.
It can be contained in an amount of 10 ⁻⁴ to 5 × 10 ⁻² mol.
The object of the present invention can be achieved by either bromide ion or iodide ion, but which of both should be used should be selected according to the use conditions.

In order to adjust the concentration of the bromide ion and / or iodide ion to the above-mentioned concentration, it may be added directly to the bleach-fixing solution itself or may be added together with the replenishing solution. It may also be partially brought from the prebath.

In the present invention, the fact that the color developer does not substantially contain sulfite ions may be added to the developer to such an extent that the photographic properties are not affected, and specifically, 0 to 0.005 m
ol / l, preferably 0-0.002 mol / l. Further, it is preferable that the color developing solution of the present invention does not substantially contain benzyl alcohol in order to further improve the desilvering property and prevent fogging and increase in stain after processing. That is, the term "substantially free of benzyl alcohol" means that the color developer is not more than 5.0 ml, preferably not more than 2 ml, and more preferably not contained at all.

In the present invention, it is preferable to add an organic preservative to the color developing solution in order to effectively prevent color contamination.

The organic preservative described in the present invention refers to all the organic compounds that reduce the deterioration rate of the aromatic primary amine color developing agent by adding it to the processing solution of the color photographic light-sensitive material. That is,
Organic compounds having a function of preventing oxidation of a color developing agent due to air, among others, hydroxylamines, hydroxamic acids, hydrazines, hydrazides, phenols, α-hydroxyketones, α-aminoketones, Sugars, monoamines, diamines, polyamines, quaternary ammonium salts, nitroxy radicals, alcohols, oximes, diamide compounds and condensed amines are particularly effective organic preservatives. These are Japanese Patent Application Nos. 61-147823, 61-173595, and 61-1.
65621, 61-188619, 61-197760, 61-186561
Issue 61-198987, Issue 61-201861, Issue 61-186559, Issue 6
1-170756, 61-188742, 61-188741, U.S. Patent No.
3615503, 2494903, JP-A-52-143020, JP-B-48-
No. 30496, etc.

Regarding the preferable organic preservatives, general formulas and specific compounds thereof are listed below, but the present invention is not limited thereto.

The amount of the following compounds added to the color developer is 0.005 mol / l to 0.5 mol / l, preferably 0.03 mol / l to 0.1 mol / l.
It is desirable to add them so that the concentration becomes.

The following are preferred as the hydroxyamines.

General formula (I) In the formula, R ¹¹ and R ¹² represent a hydrogen atom, an unsubstituted or substituted alkyl group, an unsubstituted or substituted alkenyl group, an unsubstituted or substituted aryl group, or a heteroaromatic group. R
¹¹ and R ¹² are not hydrogen atoms at the same time, and may be linked to each other to form a heterocycle together with a nitrogen atom.

It is preferable that R ¹¹ and R ¹² are an alkyl group or an alkenyl group, and the carbon number is preferably 1 to 10, and particularly preferably 1 to 5. Examples of the nitrogen-containing heterocycle formed by connecting R ¹¹ and R ¹² include a piperidyl group, a pyrrolidylyl group, an N-alkylpiperazyl group, a morpholyl group, an indolinyl group, and a benztriazole group.

Preferred substituents of R ¹¹ and R ¹² are a hydroxy group, an alkoxy group, an alkyl or aryl sulfonyl group, an amide group,
A carboxy group, a cyano group, a sulfo group, a nitro group and an amino group.

Examples of compound (I) are shown below.

Compound example The following are preferable hydroxamic acids.

General formula (II) In the formula, A ²¹ is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted amino group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted alkoxy group, a substituted Alternatively, it represents an unsubstituted aryloxy group, a substituted or unsubstituted carbamoyl group, a substituted or unsubstituted sulfamoyl group, an acyl group, a carboxy group, a hydroxyamino group, or a hydroxyaminocarbonyl group. Examples of the substituent include a halogen atom, an aryl group, an alkyl group, an alkoxy group, and the like.

Preferably A ²¹ is a substituted or unsubstituted alkyl group,
An aryl group, an amino group, an alkoxy group, and an aryloxy group. Particularly preferable examples are a substituted or unsubstituted amino group, an alkoxy group and an aryloxy group.
The number of carbon atoms is preferably 1-10.

X ²¹ is -SO ₂ -, or represents -SO-. Preferably X ²¹ is Is.

R ²¹ represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. At this time, A
²¹ and R ²¹ may combine to form a ring structure. The substituent is the same as the substituent mentioned in A ²¹ . Preferably R ²¹
Is a hydrogen atom.

Y ²¹ represents a hydrogen atom or a group capable of becoming a hydrogen atom by a hydrolysis reaction.

Compound example The following are preferred as hydrazines and hydrazides.

General formula (III) In the formula, R ³¹ , R ³² , and R ³³ are hydrogen atoms, substituted or unsubstituted,
Represents an alkyl group, an aryl group, or a heterocyclic group,
R ³⁴ represents a hydroxy group, a hydroxyamino group, a substituted or unsubstituted alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, a carbamoyl group, or an amino group.

X ³¹ is --CO--, --SO _2- , or Represents a divalent group selected from, and n is 0 or 1. Particularly when n = 0, R ³⁴ represents a group selected from an alkyl group, an aryl group and a heterocyclic group, and R ³³ and R ³⁴ may together form a heterocycle.

In the general formula (III), R ³¹ , R ³² , and R ³³ are preferably hydrogen atoms or alkyl groups, and most preferably R ³¹ and R ³² are hydrogen atoms.

In formula (III), R ³⁴ is preferably an alkyl group, an aryl group, an alkoxy group, a carbamoyl group or an amino group. X ³¹ is preferably —CO— or —SO ₂ —,
Most preferred is -CO-.

(III-2) NH ₂ NHCH _{2 4} SO ₃ H (III-3) NH ₂ NHCH _{2 2} OH (III-6) NH ₄ NHCOCH ₃ (III-7) NH ₂ NHCOOC ₂ H ₅ (III-10) NH ₄ NHCONH ₂ (III-12) NH ₄ NHSO ₃ H (III-14) NH ₂ NHCOCONHNH ₂ (III-15) NH ₂ N (CH ₂ COOH) ₂ (III-19) The following are preferred as NH ₂ NHCH ₂ CH ₂ CH ₂ SO ₃ H phenols.

General formula (IV) In the formula, R ⁴¹ represents a hydrogen atom, a halogen atom, an alkyl group,
Aryl group, alkoxy group, aryloxy group, carboxyl group, sulfo group, carbamoyl group, sulfamoyl group, amide group, sulfonamide group, ureido group, alkylthio group, arylthio group, nitro group, cyano group, amino group, formyl group, acyl Represents a group, a sulfonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an alkoxysulfonyl group, and an aryloxysulfonyl group. When R ⁴¹ is further substituted, examples of the substituent include a halogen atom, an alkyl group, an aryl group, a hydroxyl group, an alkoxy group and the like. When two or more R ^41's are present, they may be the same or different, and when they are adjacent to each other, they may be bonded to each other to form a ring. 5-6 as the ring structure
It is a member ring and is composed of carbon atoms, hydrogen atoms, halogen atoms, oxygen atoms, nitrogen atoms, sulfur atoms and the like, and may be saturated or unsaturated.

R ⁴² represents a hydrogen atom or a hydrolyzable group.
Further, m and n are integers from 1 to 5, respectively.

In formula (IV), preferred R ⁴¹ is an alkyl group,
A halogen group, an alkoxy group, an alkylthio group, a carboxyl group, a sulfo group, a carbamoyl group, a sulfamoyl group, an amino group, an amide group, a sulfonamide group, a nitro group, and a cyano group. Of these, an alkoxy group, an alkylthio group, an amino group and a nitro group are particularly preferable, and these are more preferably at the ortho position or para position of the (OR ⁴² ) group. The carbon number of R ⁴¹ is preferably 1 to 10, and particularly preferably 1 to 6.

Preferred R ⁴² is a hydrogen atom or a carbon number of 1 to 5
Up to a hydrolyzable group. Further, when there are two or more (OR ⁴² ) groups, it is more preferable that they are located in the ortho position or the para position with respect to each other.

The following are preferred as α-hydroxyketones and α-aminoketones.

General formula (V) In the formula, R ⁵¹ represents a hydrogen atom, a substituted or unsubstituted alkyl group, an aryl group, an alkoxy group, an aryloxy group or an amino group, and R ⁵² represents a hydrogen atom, a substituted or unsubstituted alkyl group or an aryl group. R ⁵¹ and R ⁵² may together form a carbocycle or a heterocycle. X ⁵¹ represents a hydroxyl group or a substituted or unsubstituted amino group.

In general formula (V), R ⁵¹ is preferably a hydrogen atom, an alkyl group, an aryl group or an alkoxy group, and R ⁵² is preferably a hydrogen atom or an alkyl group.

Sugars are also preferred organic preservatives.

Sugars (also called carbohydrates) consist of monosaccharides and polysaccharides,
Many have the general formula C _n H _2m O _m . The monosaccharides are generally referred to as aldehydes or ketones of polyhydric alcohols (referred to as aldose and ketose, respectively) and their reduced derivatives, oxidized derivatives, dehydrated derivatives, and a wider range of derivatives such as amino sugars and thio sugars. In addition, the polysaccharide refers to a product obtained by dehydration condensation of two or more of the above-mentioned monosaccharides.

Among these sugars, more preferable ones are aldoses having a reducing aldehyde group, and derivatives thereof, and particularly preferable ones are those corresponding to monosaccharides.

The following can be mentioned as monoamines.

General formula (VII) In the formula, R ⁷¹ , R ⁷² and R ⁷³ represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an aralkyl group or a heterocyclic group. Where R ⁷¹ and R ⁷² , R ⁷¹ and R ⁷³ or R ⁷² and R ⁷³
May be linked together to form a nitrogen-containing heterocycle.

Here, R ⁷¹ , R ⁷² , and R ⁷³ may have a substituent. R
^{As 71} , R ⁷² and R ⁷³ , a hydrogen atom and an alkyl group are particularly preferable.

VII-1 NCH ₂ CH ₂ OH) ₃ VII-2 H ₂ NCH ₂ CH ₂ OH VII-3 NHCH ₂ CH ₂ OH) ₂ VII-10 (HOCH ₂ CH _{2 2} NCH ₂ CH ₂ SO ₂ CH ₃ VII-11 HNCH ₂ COOH) ₂ VII-13 H ₂ NCH ₂ CH ₂ SO ₂ NH ₂ VII-14 H ₂ N-CCH ₂ OH) ₂ The following diamines are preferred.

General formula (VIII) In the formula, R ⁸¹ , R ⁸² , R ⁸³ , and R ⁸⁴ represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an aralkyl group, or a heterocyclic group.

R ⁸⁵ represents a divalent organic group, specifically an alkylene group, an arylene group, an aralkylene group, an alkenylene group or a heterocyclic group.

R ⁸¹ , R ⁸² , R ⁸³ , and R ⁸⁴ are particularly preferably a hydrogen atom or an alkyl group, and R ⁸⁵ is particularly preferably an alkylene group.

VIII-2 (HOCH ₂ CH _{2 2} NCH ₂ CH ₂ NCH ₂ CH ₂ OH) ₂ VIII-4 H ₂ NCH ₂ CH ₂ NCH ₂ CH ₂ OH) ₂ The following are preferable polyamines.

General formula (IX) In the formula, R ⁹¹ , R ⁹² , R ⁹³ and R ⁹⁴ are a hydrogen atom, an alkyl group,
It represents an alkenyl group, an aryl group, an aralkyl group or a heterocyclic group.

R ⁹⁵ , R ⁹⁶ , and R ⁹⁷ represent a divalent organic group, and specifically have the same meaning as R ^{85 in the} general formula (VIII).

R ⁹¹ and R ⁹² R represents a linking group composed of —O—, —S—, —CO—, —SO ₂ —, —SO— or a combination of these linking groups;
⁹⁸ is synonymous with R ⁹¹ , R ⁹² , R ⁹³ , and R ⁹⁴ . m represents 0 or an integer of 1 or more.

(The upper limit of m is not particularly limited and may be a high molecular weight as long as the compound is water-soluble, but usually m is preferably in the range of 1 to 3) IX-2 (HOCH ₂ CH _{2 2} NCH ₂ CH ₂ OCH ₂ CH ₂ NCH ₂ CH ₂ OH) ₂ IX-6 H ₂ NCH ₂ CH ₂ NH _n H n = 500,20,000 The following are preferred as quaternary ammonium salts.

General formula (X)(In the formula, R¹⁰¹Represents an n-valent organic group, R¹⁰², R¹⁰³And R
¹⁰⁴Represents a monovalent organic group. R¹⁰², R¹⁰³And R¹⁰⁴Out of
Quaternary ammonium atom with at least two groups bonded
It may form a heterocycle containing. n is an integer of 1 or more
And X Represents a counter anion) R¹⁰², R¹⁰³And R¹⁰⁴Particularly preferred monovalent groups are substituted or
Is an unsubstituted alkyl group, R¹⁰², R¹⁰³And R¹⁰⁴Small
At least one is a hydroxyalkyl group or an alkoxyl
Most preferred is a kill group or a carboxyalkyl group.
Good n is preferably an integer of 1 to 3, more preferably 1
Or 2.

The following are preferred as the nitroxy radicals.

General formula (XI) R ¹¹¹ and R ¹¹² each represent a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group. Further, these alkyl group, aryl group or heterocyclic group may have a substituent.
Examples of such a substituent include a hydroxy group, an oxo group, a carbamoyl group, an alkoxy group, a sulfamoyl group, a carboxy group and a sulfo group. Examples of the heterocyclic group include a pyridyl group and a piperidyl group.

Preferably, R ¹¹¹ and R ¹¹² are a substituted or unsubstituted aryl group or a tertiary alkyl group (eg, t-butyl group).

(Compound example) The following alcohols are preferable.

General formula (XII) In the formula, R ¹²¹ represents a hydroxy-substituted alkyl group, and R ¹²²
Represents an unsubstituted alkyl group or a group similar to R ¹²¹ . R ¹²³
Represents a hydrogen atom or a group similar to R ¹²² . X ¹²¹ is a hydroxy group, a carboxyl group, a sulfo group, a nitro group, an unsubstituted or hydroxy-substituted alkyl group, an unsubstituted or substituted,
It represents an amide group or a sulfonamide group.

In the general formula (XII), X ¹²¹ is preferably a hydroxy group, a carboxyl group or a hydroxyalkyl group.

XII-4 HO-CHCH ₂ OH) ₂ XII-5 (HO-CH _{2 3} COOH XII-6 CCH ₂ OH) ₄ XII-7 (HOCH _{2 3} C-CH ₃ XII-8 (HOCH _{2 3} C-NHCOCH ₃ The following alcohols are preferable.

General formula (XIII) In the formula, R ¹³¹ and R ¹³³ each represent a hydrogen atom or an alkyl group, R ¹³² represents a hydrogen atom, a hydroxyl group, an alkyl group or an alkoxy group, and n represents a positive integer up to 500.

The alkyl group represented by R ¹³¹ , R ¹³² and R ¹³³ preferably has 5 or less carbon atoms, and more preferably 2 or less carbon atoms. R ¹³¹ , R ¹³² , and R ¹³³ are very preferably hydrogen atoms or methyl groups, and most preferably hydrogen atoms.

n is preferably a positive integer of 3 or more and 100 or less,
The case of 3 or more and 30 or less is more preferable.

XIII-1 HOCH ₂ CH ₂ O ₄ OH XIII-2 CH ₃ OCH ₂ CH ₂ O ₃ OH XIII-3 CH ₃ OCH ₂ CH ₂ O ₂ OCH _{2 XIII-5 HOCH 2 CH 2 OCH} 3 XIII-6 C 2 H 5 OCH 2 CH 2 O 2 OH XIII-7 HOCH 2 CH 2 O n H average molecular weight of about _{300 XIII-8 HOCH 2 CH 2} O n H 〃 about 800 XIII-9 HOCH ₂ CH ₂ O _n H 〃 about 3000 XIII-10 HOCH ₂ CH ₂ O _n H 〃 about 8000 The following oximes are preferable.

General formula (XIV) In the formula, R ¹⁴¹ and R ¹⁴² each represent a hydrogen atom, a substituted or unsubstituted alkyl group, and a substituted or unsubstituted aryl group. Further, R ¹⁴¹ and R ¹⁴² may be the same or different, and these groups may be linked.

Preferred as R ¹⁴¹ and R ¹⁴² in the general formula (XIV) are a halogen group, a hydroxyl group, an alkoxyl group,
Amino group, carboxyl group, sulfo group, phosphonic acid group,
And an alkyl group substituted with a nitro group, and an unsubstituted alkyl group.

Further, the total number of carbon atoms in the general formula (XIV) is preferably 30 or less, and more preferably 20 or less.

The following are preferred as the diamide or disulfonamide.

General formula (XV) In the formula, X ¹⁵¹ and X ¹⁵² represent —CO— or —SO ₂ —, and R ¹⁵¹ , R ¹⁵² , R ¹⁵³ , R ¹⁵⁴ , R ¹⁵⁵ and R ¹⁵⁶ represent a hydrogen atom, an unsubstituted or substituted alkyl group. , R ¹⁵⁷ represents an unsubstituted or substituted alkylene group, an unsubstituted or substituted arylene group and an unsubstituted or substituted aralkylene group. m ¹ , m ² and n represent 0 or 1.

The following are preferred as _{XV-6 H 2 NSO 2 NHSO} 2 NH 2 condensed ring amines.

General formula (XVI) In the formula, X represents a trivalent atom group necessary for completing the condensed ring, and R ¹ and R ² represent an alkylene group, an arylene group, an alkenylene group or an aralkylene group.

Here, R ¹ and R ² may be the same or different from each other.

Among the general formula (XVI), the particularly preferable one is the general formula (1
-A) and compounds represented by (1-b).

In the formula, X ¹ represents N or CH. R ¹ and R ² are represented by the general formula (XV
As defined in I), R ³ is the same group as R ¹ , R ² , or Represents

In the general formula (1-a), X ¹ is preferably N.
The carbon number of R ¹ , R ² and R ³ is preferably 6 or less, and 3
The case of the following is more preferable, and the case of 2 is the most preferable.

R ¹ , R ² and R ³ are preferably an alkylene group or an arylene group, and most preferably an alkylene group.

In the formula, R ¹ and R ² are defined as in the general formula (XVI).

In general formula (1-b), the carbon number of R ¹ and R ² is preferably a 6-len group or an arylene group, and most preferably an alkylene group.

Among the compounds represented by formula (1-a) and (1-b), the compound represented by formula (1-a) is particularly preferable.

Many compounds of general formula (XVI) according to the present invention can be easily obtained as commercial products.

These preservatives are preferably used in combination of two or more in view of their preservative performance. Particularly, at least one compound selected from the general formulas (I) to (VI) and the general formulas (VII) to (XVI) are used. A combination of at least one compound selected is preferred. Furthermore,
One selected from the general formulas (I) and (III) and the general formula (VI
One kind of combination selected from I) and (XVI) is particularly preferable.

The color developer used in the present invention will be described below.

The color developing solution used in the present invention contains a known aromatic primary amine color developing agent. A preferred example is a p-phenylenediamine derivative, and representative examples thereof are shown below, but the invention is not limited thereto.

D-1 N, N-diethyl-p-phenylenediamine D-2 4- [N-ethyl-N- (β-hydroxyethyl) amino] aniline D-3 2-methyl-4- [N-ethyl-N- (Β-Hydroxyethyl) amino] aniline D-4 4-amino-3-methyl-N-ethyl-N-
(Β-Methanesulfonamidoethyl) -aniline Further, these p-phenylenediamine derivatives may be salts such as sulfuric acid hydrochloride, hydrochloride and p-toluenesulfonate. The amount of the aromatic primary amine developing agent used is preferably about 0.1 g to about 20 g, and more preferably about 0.5 g to about 10 g per developing solution.

The color developer used in the present invention preferably has a pH of 9 to 1.
2, more preferably from 9 to 11.0, and the color developing solution may contain other known developing solution component compounds.

In order to maintain the above pH, it is preferable to use various buffers. As the buffer, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, disodium phosphate, dipotassium phosphate, sodium borate, potassium borate, tetraborate Sodium (borax), potassium tetraborate, o-
Sodium hydroxybenzoate (sodium salicylate), potassium o-hydroxybenzoate, 5-sulfo-
Examples thereof include sodium 2-hydroxybenzoate (tonalium 5-sulfosalicylate) and potassium 5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate).

The amount of the buffer added to the color developing solution is preferably 0.1 mol / l or more, and particularly preferably 0.1 mol / l to 0.4 mol / l.

In addition, various chelating agents can be used in the color developing solution as a precipitation preventing agent for calcium and magnesium, or for improving the stability of the color developing solution.

Specific examples are shown below, but the present invention is not limited thereto.

-Nitrilotriacetic acid-Diethylenetriaminepentaacetic acid-Ethylenediaminetetraacetic acid-Triethylenetetraminehexaacetic acid-N, N, N-trimethylenephosphonic acid-Ethylenediamine-N, N, N ', N'-tetramethylenephosphonic acid-1,3 -Diamino-2-propanoltetraacetic acid-Transcyclohexanediaminetetraacetic acid-Nitrilotripropionic acid-1,2-diaminopropanetetraacetic acid-Hydroxyethyliminodiacetic acid-Glycol ether diaminetetraacetic acid-Hydroxyethylenediaminetriacetic acid-Ethylenediamineorthohydroxyphenyl Acetic acid 2-phosphonobutane-1,2,4-tricarboxylic acid 1-hydroxyethylidene-1,1-diphosphonic acid N, N'-bis (2-hydroxybenzyl) ethylenediamine-N, N'-diacetic acid If necessary, use two or more chelating agents in combination. It may be.

The amount of these chelating agents added may be an amount sufficient to block the metal ions in the color developing solution. Eg 1
It is about 0.1g to 10g.

If necessary, any development accelerator can be added to the color developing solution.

As a development accelerator, Japanese Examined Patent Publication Nos. 37-16088 and 37-5987
Nos. 38-7826, 44-12380, 45-9019, and thioether compounds represented by U.S. Pat. No. 3,813,247, and JP-A Nos. 52-49829 and 50-15554.
-Phenylenediamine compounds, JP-A-50-137726,
JP-B-44-30074, JP-A-56-156826 and JP-A-52-43429
, Etc., quaternary ammonium salts, US Pat.
P-aminophenols described in 2,610,122 and 4,119,462, U.S. Pat. Nos. 2,494,903, 3,128,182, and 4,
230,796, 3,253,919, Japanese Patent Publication No. 41-11431, U.S. Pat.Nos. 2,482,546, 2,596,926 and 3,582,346, etc., amine compounds described in Japanese Patent Publications 37-16088, 42-252.
01, U.S. Patent No. 3,128,183, Japanese Patent Publication No. 41-11431, 4
2-23883 and U.S. Pat. No. 3,532,501, and other polyalkylene oxides, other 1-phenyl-3-pyrazolidones, hydrazines, mesoionic compounds, ionic compounds, imidazoles, etc. are added as necessary. be able to.

In the present invention, any anti-capry agent can be added, if necessary. As the antifoggant, alkali metal halides such as sodium chloride, potassium bromide and potassium iodide, and organic antifoggants can be used. Examples of the organic antifoggant include benzotriazole and 6-
Nitrobenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chloro-benzotriazole, 2-
Representative examples thereof include nitrogen-containing heterocyclic compounds such as thiazolyl-benzimidazole, 2-thiazolylmethyl-benzimidazole, indazole, hydroxyazaindolizine and adenine.

The color developer used in the present invention preferably contains a fluorescent whitening agent. As the fluorescent whitening agent, 4,4'-diamino-2,2'-disulfostilbene compound is preferable. The addition amount is 0 to 5 g / l, preferably 0.1 to 4 g / l.

If necessary, various surfactants such as alkyl sulfonic acid, aryl phosphonic acid, aliphatic carboxylic acid and aromatic carboxylic acid may be added.

The processing temperature of the color developer of the present invention is preferably 20 to 50 ° C.
30-40 ° C. The processing time is 20 seconds to 5 minutes, preferably 30 seconds to 2 minutes. The amount of replenishment is preferably as small as possible, but it is ^{20 to} 600 ml, preferably 50 to 300 ml per 1 m ^{2 of} the light-sensitive material. More preferably, it is 100 ml to 200 ml.

Next, the bleach-fix solution used in the present invention will be described.

As the bleaching agent used in the bleach-fixing solution used in the present invention, any bleaching agent can be used,
In particular, organic complex salts of iron (III) (for example, aminopolycarboxylic acids such as ethylenediaminetetraacetic acid and diethylenetriaminepentaacetic acid, complex salts of aminopolyphosphonic acid, phosphonocarboxylic acid and organic phosphonic acid) or citric acid, tartaric acid, malic acid, etc. Organic acids; persulfates; hydrogen peroxide and the like are preferred.

Of these, organic complex salts of iron (III) are particularly preferable from the viewpoint of rapid processing and prevention of environmental pollution. Aminopolycarboxylic acids, aminopolyphosphonic acids, or organic phosphonic acids or salts thereof useful for forming organic complex salts of iron (III) are listed as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, 1,3-diaminopropane. Tetraacetic acid, propylenediaminetetraacetic acid, nitrilotriacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, iminodiacetic acid, glycol etherdiaminetetraacetic acid and the like can be mentioned. These compounds may be sodium, potassium, lithium or ammonium salts. Among these compounds, ethylenediaminetetraacetic acid,
Iron (III) complex salts of diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, 1,3-diaminopropanetetraacetic acid and methyliminodiacetic acid are preferred because of their high bleaching power.

These ferric ion complex salts may be used in the form of complex salts, and ferric salts such as ferric sulfate, ferric chloride, ferric nitrate, ferric ammonium sulfate, ferric phosphate. And a chelating agent such as aminopolycarboxylic acid, aminopolyphosphonic acid or phosphonocarboxylic acid may be used to form a ferric ion complex salt in a solution. Also, the chelating agent is second
It may be used in excess to form the iron ion complex salt. Among the iron complexes, aminopolycarboxylic acid iron complexes are preferable, and the addition amount thereof is 0.01 to 1.0 mol / l, preferably 0.05 to 0.5.
It is 0 mol / l.

In the bleach-fixing solution, various compounds can be used together as a bleaching accelerator in addition to the halide ion of the present invention. For example, U.S. Patent No. 3,893,858, German Patent No. 1,290,812, JP-A-53-95630, Research Disclosure No. 17129 (July 1978).
Compounds having a mercapto group or a disulfide bond described in JP-B-45-8506, JP-A-52-20832, and 53-
32735 and the thiourea compounds described in U.S. Pat. No. 3,706,561 and the like are preferable because of their excellent bleaching power.

In addition, the bleach-fixing solution used in the present invention contains, if necessary, boric acid, borax, sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, phosphorous acid, phosphoric acid, sodium phosphate, citric acid, sodium citrate, tartaric acid. It is possible to add one or more kinds of inorganic acids, organic acids and their alkali metal or ammonium salts having a pH buffering ability such as, or corrosion inhibitors such as ammonium nitrate and guanidine.

The fixing agents used in the bleach-fixing solution according to the present invention are known fixing agents, that is, thiosulfates such as sodium thiosulfate and ammonium thiosulfate; thiocyanates such as sodium thiocyanate and ammonium thiocyanate; ethylenebisthioglycol. Acids, thioether compounds such as 3,6-dithia-1,8-octanediol, and water-soluble silver halide solubilizers such as thioureas, which may be used alone or in admixture of two or more. it can. Further, a special bleach-fixing solution containing a combination of a fixing agent described in JP-A-55-155354 and a large amount of a halide such as potassium iodide can be used. In the present invention, it is preferable to use thiosulfate, particularly ammonium thiosulfate. The amount of the fixing agent per 1 is preferably 0.3 to 2 mol, more preferably 0.5 to 1.0 mol. The pH range of the bleach-fixing solution is preferably 3-10, more preferably 5-9.
Is particularly preferable.

Further, the bleach-fixing solution may contain various other fluorescent whitening agents, defoaming agents or surfactants, polyvinylpyrrolidone, organic solvents such as methanol.

The bleach-fixing solution according to the present invention is a preservative such as sulfite (eg, sodium sulfite, potassium sulfite, ammonium sulfite, etc.), bisulfite (eg, ammonium bisulfite, sodium bisulfite, potassium bisulfite, etc.). ), Metabisulfite (eg, potassium metabisulfite, sodium methyl bisulfite, ammonium metabisulfite, etc.) and the like. These compounds are preferably contained in an amount of about 0.02 to 0.50 mol / l in terms of sulfite ion, more preferably 0.04 to
It is 0.40 mol / l.

As a preservative, it is common to add sulfite, but in addition, ascorbic acid and carbonyl bisulfite adduct,
Sulfinic acids described in Japanese Patent Application No. 62-142941, etc., or
A carbonyl compound or the like may be added.

Further, a buffering agent, a fluorescent whitening agent, a chelating agent, a defoaming agent, an antifungal agent and the like may be added as required.

The shorter the processing time of the desilvering step in the present invention, the more remarkable the effect of the present invention, and the desilvering step time is 2 minutes or less, more preferably 1 minute or less.

The silver halide color photographic light-sensitive material used in the present invention is generally washed with water and / or stabilized after desilvering such as bleach-fixing.

The amount of rinsing water in the rinsing process depends on the characteristics of the light-sensitive material (for example, depending on the materials used such as couplers), the application, the temperature of the rinsing water, the number of rinsing tanks (the number of tiers), the replenishment method such as countercurrent and forward flow, and various other conditions. It can be set in a wide range. Among these, the relationship between the number of washing tanks and the amount of water in the multi-stage countercurrent system is as follows: Journal of the Society of Motion Picture and Tel.
evision Engineers) Volume 64, p.248-253 (May 1955 issue). Usually, the number of stages in the multi-stage countercurrent system is preferably 2 to 6, and particularly preferably 2 to 4.

According to the multi-stage countercurrent method, the amount of washing water can be greatly reduced, and for example, 1 or less, preferably 0.5 l or less per 1 m ^{2 of the} light-sensitive material is possible, and the effect of the present invention is remarkable, but in the tank Due to an increase in the residence time of water, bacteria propagate and problems such as adherence of the produced floating substances to the light-sensitive material occur. In the processing of the color light-sensitive material of the present invention, the method of reducing calcium and magnesium described in Japanese Patent Application No. 61-131632 can be used very effectively as a solution to such a problem. Further, isothiazolone compounds and siabendazoles described in JP-A-57-8542, 61-120
Chlorinated germicides such as chlorinated sodium isocyanurate described in No. 145, benzotriazole described in Japanese Patent Application No. 60-105487, copper ion and others Hiroshi Horiguchi "Chemistry of antibacterial and antifungal agents", Hygiene Society It is also possible to use the bactericides described in "Microbial Sterilization, Sterilization, and Antifungal Technologies", edited by the Society for Antibacterial and Antifungal Society, "Encyclopedia of Antibacterial and Antifungal Agents".

Further, for washing water, a surfactant as a draining agent and a chelating agent typified by EDTA as a water softener can be used.

It is also possible to carry out treatment with the stabilizing solution directly after the above washing step or without going through the washing step. A compound having an image stabilizing function is added to the stabilizing solution. For example, an aldehyde compound typified by formalin or a film pH suitable for stabilizing a dye is used.
A buffering agent for adjusting the concentration and an ammonium compound can be used. Further, in order to prevent the growth of bacteria in the liquid and impart antifungal property to the processed light-sensitive material, the above-mentioned various bactericides and antifungal agents can be used.

Further, a surfactant, a fluorescent whitening agent, and a hardener can be added. In the processing of the light-sensitive material of the present invention, when the stabilization is directly carried out without undergoing a washing step, JP-A-57-854
All known methods described in No. 3, No. 58-14834, No. 60-220345, etc. can be used.

In addition, it is also a preferred embodiment to use a chelating agent such as 1-hydroxyethylidene-1,1-diphosphonic acid or ethylenediaminetetramethylenephosphonic acid, or a magnesium or bismuth compound.

In addition, the stabilizing liquid can be drastically reduced (1 or less, more preferably 0.5 l or less) by adopting a multi-stage countercurrent system like the washing water. Replenishment of washing water or stabilizing solution may be continuous or intermittent. In the latter case, the processing is performed according to the processing amount or at regular time intervals.

The washing step or stabilizing step of the present invention has a pH of 4 to 10,
It is preferably 5 to 8. Although the temperature can be set variously depending on the use and characteristics of the light-sensitive material, it is generally 15 to 45 ° C, preferably
20 to 40 ° C. The time can be set arbitrarily, but the shorter the time, the more remarkable the effect of the present invention, and preferably 30 seconds to 2
Minutes, more preferably 30 seconds to 1 minute 30 seconds. The smaller the replenishment amount, the more preferable from the viewpoint of running cost, reduction of discharge amount, handleability, and the like, and the effect of the present invention is great.

The specific amount of replenishment is 0.5 to 50 times, preferably 3 to 40 times the carry-in amount per unit area from the pre-bath.

The liquid used in the washing and / or stabilizing step can be further used in the previous step. As an example of this, overflow of washing water reduced by the multi-stage countercurrent direction is caused to flow into the bleach-fixing bath of the preceding bath, and the bleach-fixing bath is replenished with a concentrated solution,
It is possible to reduce the amount of waste liquid.

In the present invention, the total time of the bleach-fixing step and the washing or stabilizing step is preferably 3 minutes or less.

The method of the present invention is a process using a color developing solution,
It can be applied to any processing step. For example, it can be applied to the processing of color paper, color reversal paper, color direct positive light-sensitive material, color positive film, color negative film, color reversal film, etc. Application is preferred.

The silver halide emulsion of the light-sensitive material used in the present invention may have any halogen composition such as silver iodobromide, silver bromide, silver chlorobromide and silver chloride. However, in the case of performing rapid processing or low replenishment processing, a silver chlorobromide emulsion or a silver chloride emulsion containing 80 mol% or more of silver chloride is preferable, and when the content of silver chloride is 90 to 100 mol%. Is particularly preferable.
The effect of the present invention is particularly remarkable when rapid processing or low replenishment processing is performed using the above emulsion.

The silver halide grains used in the present invention may have different phases in the inside and the surface layer, may have a multi-phase structure having a junction structure, or may have a uniform phase as a whole. Moreover, they may be mixed.

The average grain size of the silver halide grains used in the present invention (in the case of spherical grains or grains close to spheres, the grain diameter is represented, and in the case of cubic grains, the edge length is represented as the grain size, is represented by the average based on the projected area. Is expressed in terms of yen) is preferably 2 μm or less and 0.1 μm or more, and particularly preferably 1.5 μm or less and 0.15 μm or more. The grain size distribution may be narrow or wide, but the value obtained by dividing the standard deviation value in the grain size distribution curve of the silver halide emulsion by the average grain size (variation rate) is within 20%, particularly preferably 15 It is preferred to use so-called monodisperse silver halide emulsions within the range of% in the present invention. Further, in order to satisfy the target gradation of the light-sensitive material, two or more kinds of monodisperse silver halide emulsions having different grain sizes in the emulsion layers having substantially the same color sensitivity (the above-mentioned monodispersity is the same). Those having a variation rate are preferable) can be mixed in the same layer or multilayer-coated in different layers. Further, two or more kinds of polydisperse silver halide emulsions or a combination of a monodisperse emulsion and a polydisperse emulsion can be used as a mixture or layers.

The silver halide grains used in the present invention may have a regular crystal such as a cube, an octahedron, a rhodohedron, and a tetradecahedron, or may have a coexisting form thereof. It may have irregular crystals such as spheres, or may have a composite form of these crystal forms. Further, an average grain may be used, and particularly, an emulsion in which tabular grains having a length / thickness ratio value of 5 to 8 or 8 or more occupy 50% or more of the total projected area of grains may be used. It may be an emulsion composed of a mixture of these various crystal forms. These various emulsions may be either a surface latent image type which forms a latent image mainly on the surface or an internal latent image type which is formed inside the grain.

The photographic emulsion used in the present invention can be prepared using the method described in Research Disclosure (RD) vol.170 Item No.17643 (I, II, III) (December 1978). it can.

The emulsion used in the present invention is usually one which has been physically ripened, chemically ripened and spectrally sensitized. Additives used in such processes are Research Disclosure Volume 176, No. 17643 (December 1978) and Volume 187, N.
No. 18716 (November 1979), and the corresponding places are summarized in the table below.

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

Various color couplers can be used in the present invention. Here, the color coupler means a compound capable of forming a dye by a coupling reaction with an oxidized product of an aromatic primary amine developing agent. Typical examples of useful color couplers are naphthol or phenol compounds, pyrazolone or pyrazoloazole compounds and open chain or heterocyclic ketomethylene compounds. Specific examples of these cyan, magenta and yellow couplers that can be used in the present invention are Research Disclosure (RD) 17643 (1978).
December 1987), section VII-D and the patent cited in 18717 (November 1979).

The color coupler incorporated in the light-sensitive material preferably has a ballast group or is polymerized to be diffusion resistant. The amount of coated silver can be reduced in the case of a two-equivalent color coupler in which a coupling active position is substituted by a leaving group, rather than a four-equivalent color coupler in which a hydrogen atom is present. It is also possible to use a coupler in which the color-forming dye has an appropriate diffusivity, a non-color-forming coupler, or a DIR coupler which releases a development inhibitor upon coupling reaction or a coupler which releases a development accelerator.

A typical example of the yellow coupler that can be used in the present invention is an oil protect type acylacetamide coupler. A specific example is U.S. Pat. No. 2,407,21.
No. 0, No. 2,875,057 and No. 3,265,506. In the present invention, it is preferable to use a 2-equivalent yellow coupler, and U.S. Pat.Nos. 3,408,194 and 3,447,9 are used.
No. 28, No. 3,933,501 and No. 4,022,620 oxygen atom desorption type yellow couplers described in JP-B-55-10739, U.S. Pat.Nos. 4,401,752, 4,326,024
No., RD18053 (April 1979), British Patent No. 1,425,020,
West German Application Publication No. 2,219,917, No. 2,261,361, No. 2,
Representative examples thereof include nitrogen atom-releasing yellow couplers described in Nos. 329,587 and 2,433,812. The α-pivaloyl acetanilide type coupler is excellent in the fastness of the color forming dye, particularly, the light fastness.
-The benzoylacetanilide type coupler provides a high color density.

Examples of the magenta coupler which can be used in the present invention include oil-protection type indazolone type or cyanoacetyl type, preferably 5-pyrazolone type and pyrazoloazole type couplers such as pyrazolotriazoles. The 5-pyrazolone-based coupler is preferably a coupler in which the 3-position is substituted with an arylamino group or an acylamino group, from the viewpoint of the hue and color density of the color forming dye, and typical examples thereof are U.S. Pat.Nos. 2,311,082 and 2,343,703. ,
No. 2,600,788, No. 2,908,573, No. 3,062,653
No. 3,152,896 and No. 3,936,015. As the leaving group of the 2-equivalent 5-pyrazolone-based coupler, the nitrogen atom leaving group described in US Pat. No. 4,310,619 or the arylthio group described in US Pat. No. 4,351,897 is preferable. Further, the 5-pyrazolone-based coupler having a ballast group described in EP 73,636 provides a high color density.

As a pyrazoloazole-based coupler, US Pat.
Pyrazolobenzimidazoles described in 9,879, preferably pyrazolo [5,1] described in U.S. Patent No. 3,725,067.
-C] [1,2,4] triazoles, pyrazolotetrazoles described in Research Disclosure 24220 (June 1984) and Research Disclosure 24230.
(June 1984), and pyrazolopyrazoles. The imidazo compound described in European Patent 119,741 [1,2-
b] Pyrazoles are preferred, and the pyrazolo [1,5-b] [1,2,4] triazoles described in EP 119,860 are particularly preferred.

As the cyan coupler which can be used in the present invention, in addition to the cyan coupler represented by the general formula (C), oil protect type naphthol type and phenol type couplers can be used in combination, and the naphthol type couplers described in US Pat. No. 2,474,293, Preferably U.S. Pat.
Representative examples are the oxygen atom-elimination type two-equivalent naphthol couplers described in 4,146,396, 4,228,233 and 4,296,200. Further, specific examples of the phenol-based coupler are described in U.S. Patent Nos. 2,369,929 and 2,801,1.
No. 71, No. 2,772,162, No. 2,895,826 and the like.

The graininess can be improved by using a coupler in which the color forming dye has an appropriate diffusibility. Such dye-diffusing couplers are described in U.S. Patent No. 4,366,237 and British Patent No. 2,1.
Specific examples of magenta couplers are described in 25,570, and specific examples of yellow, magenta or cyan couplers are described in EP 96,570 and West German Patent Application Publication No. 3,234,533.

The dye-forming coupler and the above-mentioned special coupler may form a dimer or higher polymer. Typical examples of polymerized dye forming couplers are described in US Pat. Nos. 3,451,820 and 4,080,211. Specific examples of polymerized magenta couplers are described in British Patent No. 2,102,173 and U.S. Patent No. 4,367,282.

The various couplers used in the present invention can be used in combination of two or more kinds in the same layer of the light-sensitive layer in order to satisfy the properties required for the light-sensitive material, and the same compound can be used in two or more different layers. Can also be introduced.

The coupler used in the present invention can be introduced into the light-sensitive material by various known dispersion methods. Examples of the high boiling point organic solvent used in the oil-in-water dispersion method are described in US Pat. No. 2,322,027. Further, the steps of the latex dispersion method, effects, specific examples of latex for impregnation, U.S. Pat.
363, West German Patent Application (OLS) Nos. 2,541,274 and
It is described in No. 2,541,230.

The standard amount of the color coupler used is in the range of 0.001 to 1 mol per mol of the light-sensitive silver halide, preferably 0.01 to 0.5 mol for the yellow coupler, 0.003 to 0.3 mol for the magenta coupler, and 0.003 to 0.3 mol for the cyan coupler. It is 0.002 to 0.3 mol.

The photographic light-sensitive material used in the present invention is applied to a commonly used plastic film (cellulose nitrate, cellulose acetate, polyethylene terephthalate, etc.), a flexible support such as paper or a rigid support such as glass. See Research Disclosure, Volume 176, Item 17643, Item XV (p.27), for details on the support and coating method.
It is described in Section XVII (p.28) (December 1978 issue).

In the present invention, a reflective support is preferably used.
The "reflective support" is one which enhances the reflectivity and makes the dye image formed on the silver halide emulsion layer clear, and such a reflective support includes titanium oxide, zinc oxide, Examples include those coated with a hydrophobic resin containing a light reflecting substance such as calcium carbonate and calcium sulfate dispersed therein, and those using a hydrophobic resin containing a light reflecting substance dispersed therein as a support.

(Examples) Hereinafter, the present invention will be described in more detail by showing specific examples of the present invention. However, the present invention is not limited to the following examples.

Example 1 A multilayer color photographic printing paper A having the following layer constitution was prepared on a paper support laminated on both sides with polyethylene.

The coating solution is prepared by mixing and dissolving an emulsion, various chemicals, and an emulsified dispersion of a coupler. The respective preparation methods are shown below.

(Preparation of coupler emulsion) Yellow coupler (ExY) 19.1 g and color image stabilizer (Cpd
-1) 4.4g ethyl acetate 27.2cc and solvent (Solv-1)
Add 7.7 cc to dissolve, and add this solution to 10% sodium dodecylbenzenesulfonate 8 cc 10% gelatin aqueous solution 185
It was emulsified and dispersed in cc.

In the same manner, emulsions for magenta, cyan and the intermediate layer were prepared.

Next, a method for adjusting the emulsion used in this example is shown.

(Blue sensitive emulsion) (2 solutions) Sulfuric acid (IN) 24cc (Liquid 1) was heated to 76 ° C., and (2nd liquid) and (3rd liquid) were added.

Then, (4 solution) and (5 solution) were added simultaneously spending 10 minutes.

After another 10 minutes, (6 solution) and (7 solution) were added simultaneously spending 35 minutes. Five minutes after the addition, the temperature was lowered and the mixture was desalted. Water and dispersed gelatin were added to adjust the pH to 6.3 to obtain a monodisperse cubic silver chloride emulsion having an average grain size of 1.1 μm and a coefficient of variation (standard deviation divided by the average grain size: s / d) of 0.10.

0.6 kg of the spectral sensitizing dye for blue (S-1) was added to 1.0 kg of this emulsion.
% Cc solution was added, and 0.05 μg AgBr ultrafine grain emulsion was added at a ratio of 0.5 mol% to the host AgCl emulsion, and mixed and aged at 58 ° C. for 10 minutes. After that, sodium thiosulfate is added for optimal chemical sensitization and stabilizer (St
b-1) was added at 10 ^-4 mol / mol Ag.

(Green sensitive emulsion) (9 solutions) Sulfuric acid (1N) 24 ml (10 solutions) Compound A (1%) 3 ml (8 liquid) was heated to 52 ° C., and (9 liquid) and (10 liquid) were added. After that, (11 solution) and (12 solution) were spent for 14 minutes and added simultaneously. After a further 10 minutes, (13 solution) and (14 solution) were added simultaneously spending 15 minutes.

The sensitizing dye (S-2) was added to this emulsion in an amount of 4 × 10 ^-4 mol per mol of silver halide, and then the following (15th solution) was added over 10 minutes. Salted

Add water and dispersed gelatin, adjust pH to 6.2, Monodispersed cubic silver chloride emulsion with an average grain size of 0.48 μm and a coefficient of variation (standard deviation divided by the average grain size: s / d) of 0.10. Got

Further, (Stb-1) was added as a stabilizer in an amount of 5 × 10 ^-4 mol per mol of silver halide.

The red-sensitive emulsion is exactly the same as in the method for preparing the green-sensitive emulsion except that the sensitizing dye used is changed to (S-3) and the addition amount is set to 1.5 × 10 ^-4 mol per mol of silver halide. Was prepared.

(Layer Structure) The composition of each layer in Sample A is shown below. Numbers represent coating weight (g / m ² ). The silver halide emulsion represents the coating amount in terms of silver.

Support Polyethylene laminated paper [Polyethylene on the first layer side contains white pigment (TiO ₂ ) and bluish dye (ultra-blue)] First layer (blue sensitive layer) Silver halide emulsion 0.30 Gelatin 1.86 Yellow coupler (ExY) 0.82 Color image stabilizer (Cpd-1) 0.19 Solvent (Solv-1) 0.35 Second layer (color mixing prevention layer) Gelatin 0.99 Mixing prevention (Cpd-2) 0.08 Third layer (green sensitive layer) Silver halide emulsion 0.36 Gelatin 1.24 Magenta coupler (ExM1) 0.31 Color image stabilizer (Cpd-3) 0.25 Color image stabilizer (Cpd-4) 0.12 Solvent (Solv-2) 0.42 Fourth layer (UV absorbing layer) Gelatin 1.58 UV absorber (UV-1 ) 0.62 Anti-color mixing agent (Cpd-5) 0.05 Solvent (Solv-3) 0.24 Fifth layer (red sensitive layer) Silver halide emulsion 0.23 Gelatin 1.34 Cyan coupler (ExC1) 0.34 Color image stabilizer (Cpd-6) 0.17 Polymer (Cpd-7) 0.40 Solvent (Solv-4) 0.23 Sixth layer (UV Line absorption layer) Gelatin 0.53 UV absorber (UV-1) 0.21 Solvent (Solv-3) 0.08 Seventh layer (protective layer) Gelatin 1.33 Polyvinyl alcohol acrylic modified copolymer (Degree of modification 17%) 0.17 Liquid paraffin 0.03 Each layer As a hardening agent of, 1-oxy-3,5-dichloro-
5-triazine sodium salt was used.

The compounds used respectively are as follows.

(Solv-3) solvent _{O = PO-C 9 H 19} (iso)) 3 The following dyes were added to the red-sensitive layer and the green-sensitive layer to prevent irradiation.

The following compounds were added to the red-sensitive emulsion layer in an amount of 2.6 × 10 ^-3 mol per mol of silver halide.

Solv-2 O = PO-C ₈ H ₁₇ (iso)) ₃ processing After imagewise exposing the above-mentioned photosensitive material sample A, the composition of the color developing solution and the bleach-fixing solution was processed in the following processing steps using a paper processor. Was partially changed, and continuous processing (running test) was carried out until each tank was replenished with twice the capacity of the color developing tank to prepare running solutions.

The composition of each treatment liquid is as follows.

Bleach-fixing solution (same as tank solution and replenisher) Water 400ml Ammonium thiosulfate (70%) 100ml Sodium sulfite 17g Ethylenediaminetetraacetic acid iron (III) ammonium 55g Ethylenediaminetetraacetic acid disodium 5g Glacial acetic acid 9g Halide Table 1 Water 1000 ml pH (25 ℃) 5.40 Stabilizer 1-Hydroxyethylidene-1, -diphosphonic acid (60%)
1.6ml bismuth chloride 0.3g ammonia water (26%) 2.5 ml Nitrilotriacetic acid 1.0 g 5-chloro-2-methyl-4-isothiazolin-3-one 0.05g 2-octyl-4-isothiazolin-3-one 0.05g firefly Photobleaching agent (4,4′-diaminostilbene type) 1.0 g Water was added to 1000 ml pH (25 ° C.) 7.5 Next, the cyan coupler of Sample A was changed as follows to prepare Samples BF.

Sample D C-2 Sample E C-3 Sample F C-9 Samples A to F were exposed to 250 CMS through a wedge wedge and then treated with running solutions. The amount of residual silver in the Dmax portion (maximum density portion) of the treated sample was measured by fluorescent X-ray. The Dmin portion (minimum density portion) was measured for yellow density (D _B min) with a Macbeth reflection densitometer. Further, the cyan density (D _R min) of the Dmax part was measured, and then the sample was immersed in CN-16N ₂ -R manufactured by Fuji Photo Film Co., Ltd. for 4 minutes at room temperature, washed with water, dried, and then again. D _R min was measured and the cyan color development rate was determined.

The results are shown in Table 1.

Based on Table 1, when the cyan coupler of the present invention was used and the treatment of the present invention was carried out, excellent results were obtained in desilvering property, stain and color forming property.

Example 2 Sample D prepared in Example 1 was treated in the same manner as in Example 1 except that the preservative and halide were changed as shown in Table 2 below, and excellent results were obtained.

Example 3 On a paper support laminated on both sides with polyethylene, a multi-layer photographic paper G having the following layer constitution was produced. The coating liquid was prepared as follows.

(Preparation of coating solution for the first layer) Yellow couplers (ExY-1 ') and (ExY-2') 10.2 g and 9.1 g, respectively, and color image stabilizer (Cpd-1 ') 4.4 g, ethyl acetate 27.2 cc and high boiling point Solvent (Solv-1 ′) 7.7cc
(8.0 g) was added and dissolved, and this solution was dissolved in 10% sodium dodecylbenzenesulfonate 8 cc 10% gelatin aqueous solution 1
It was emulsified and dispersed in 85 cc. This emulsified dispersion and emulsion EM1 and E
M2 was mixed and dissolved, and the gelatin concentration was adjusted so that the following composition was obtained to prepare a coating solution for the first layer. The coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer. As the gelatin hardening agent for each layer, 1-oxy-3,5-dichloro-s-triazine sodium salt was used.

Further, (Cpd-2 ') was used as a thickener.

(Layer constitution) The composition of each layer is shown below. Numbers represent coating weight (g / m ² ). The silver halide emulsion represents the coating amount in terms of silver.

Support Polyethylene laminated paper [Polyethylene on the first layer side contains white pigment (TiO2) and bluish dye. ] 1st layer (blue sensitive layer) Monodispersed silver chlorobromide emulsion (EM1) spectrally sensitized with sensitizing dye (ExS-1 ') ... 0.13 Spectral sensitizing with sensitizing dye (ExS-1) Monodispersed silver chlorobromide emulsion (EM2) ...... 0.13 Gelatin ...... 1.86 Yellow coupler (ExY-1 ') ...... 0.44 Yellow coupler (ExY-2') ...... 0.39 Color image stabilizer (Cpd-1 ') …… 0.19 Solvent (Solv-1 ′) …… 0.35 Second layer (color mixing prevention layer) Gelatin …… 0.99 Color mixing inhibitor (Cpd-3 ′) …… 0.08 Third layer (green sensitive layer) Sensitizing dye (ExS -2 ', 3') spectrally sensitized monodisperse silver chlorobromide emulsion (EM3) ...... 0.05 Monodispersed silver chlorobromide spectrally sensitized with a sensitizing dye (ExS-2 ', 3') Emulsion (EM4) …… 0.11 Gelatin …… 1.80 Magenta coupler (ExM-1 ′) …… 0.39 Color image stabilizer (Cpd-4 ′) …… 0.20 Color image stabilizer (Cpd-5 ′) …… 0.02 Color image Stabilizer (Cpd-6 ') ...... 0.03 Melt (Solv-2 ') ...... 0.12 Solvent (Solv-3') ...... 0.25 Fourth layer (UV absorbing layer) Gelatin ...... 1.60 UV absorber [Cpd-7 '/ Cpd-8' / Cpd-9 ' = 3/2 /
(6: Weight ratio) …… 0.70 Color mixture inhibitor (Cpd-10 ′) …… 0.05 Solvent (Solv-4 ′) …… 0.27 Fifth layer (red sensitive layer) Sensitizing dye (ExS-4 ′, 5 ′) Dispersion-sensitized silver chlorobromide emulsion (EM5) ...... 0.07 Monodisperse silver chlorobromide emulsion (EM6) spectrally sensitized with sensitizing dye (ExS-4 ', 5') 0.16 Gelatin: 0.92 Cyan coupler (ExC-1 '): 0.32 Color image stabilizer (Cpd-8' / Cpd-9 '/ Cpd-12 = 3/4/2: weight ratio): 0.17 Dispersing polymer ( Cpd-11 ') 0.28 Solvent (Solv-2') 0.20 Sixth layer (UV absorbing layer) Gelatin 0.54 UV absorber (Cpd-7 '/ Cpd-9' / Cpd-12 '= 1 /Five/
3: Weight ratio) 0.21 Solvent (Solv-2 ') 0.08 7th layer (protective layer) Gelatin 1.33 Acrylic modified copolymer of polyvinyl alcohol (Degree of modification)
17%) ...... 0.17 Liquid paraffin ...... 0.03 At this time, as the dye for preventing irradiation,
(Cpd-13 ', Cpd-14') were used.

Further, in each layer, an emulsifying dispersant and an alkanol B (Dupont), sodium alkylbenzenesulfonate, succinic acid ester and Ma-gefacx F-120 (manufactured by Dainippon Ink and Chemicals) were used as coating aids. (Cpd-15 ', 16') was used as a stabilizer for silver halide.

Details of the emulsion used are as follows.

The structural formulas of the compounds used are as follows.

Solv-1 ′ dibutyl phthalate Solv-2 ′ tricresyl phosphate Solv-3 ′ trioctyl phosphate Solv-4 ′ trinonyl phosphate After the image-wise exposure of the above light-sensitive material sample G, the following treatment was performed using a Fuji color paper processor PP600. Each step (running test) was carried out until the composition was replenished continuously in the process until the tank was replenished with twice the capacity of the color developing tank, but the compositions of the color developing solution and the bleach-fixing solution were changed as shown in Table 3.

The composition of each treatment liquid is as follows.

Rinsing liquid ion-exchanged water (calcium, magnesium each 3ppm or less) these results in Table 3 (residual silver amount, D _B min and color index)
Indicates.

According to the present invention, the residual silver amount, DBmin and the coloring rate of the cyan dye are good, but it is particularly effective when benzyl alcohol is not present (No. 5, 6, 7, 8).

(Effect of the Invention) According to the method of the present invention, color stain, desilvering property, and color reversion property are improved.

 ─────────────────────────────────────────────────── ─── Continuation of front page (56) Reference JP-A-56-94349 (JP, A) JP-A-52-134433 (JP, A) JP-A-61-112145 (JP, A) JP-A-51- 87036 (JP, A) JP-A-59-166956 (JP, A) JP-B-49-11572 (JP, B1) British patent 926569 (GB, A)

Claims (2)

[Claims] 1. A processing method in which a silver halide color photographic light-sensitive material is exposed to light and then processed with a color developing solution, and subsequently with a bleach-fixing solution, wherein the color developing solution contains substantially no sulfite ion. And the bleach-fixing solution contains 1 × 10 ⁻² to 2 mol of bromide ion and / or 5 × 10 ⁻⁴ per one.
A silver halide color containing up to 5 × 10 ^-2 mol of iodide ion, and the color photographic light-sensitive material contains at least one cyan coupler represented by the following general formula (C). Processing method of photographic light-sensitive material. General formula (C) (In the formula, R _a represents an alkyl group, a cycloalkyl group, an aryl group, an amino group or a heterocyclic group. R _b represents an acylamino group or an alkyl group having 2 or more carbon atoms. R _c represents a hydrogen atom or a halogen atom. Represents an alkyl group or an alkoxy group, and R _c may combine with R _b to form a ring.
Z _a represents a hydrogen atom, a halogen atom or a group capable of splitting off upon reaction with an oxidized product of an aromatic primary amine color developing agent. ) 2. The method for processing a silver halide color photographic light-sensitive material according to claim 1, wherein the color developing solution contains substantially no benzyl alcohol.