JPH07117721B2 - Processing method of silver halide color photographic light-sensitive material - Google Patents

Description

The present invention relates to a method for processing a silver halide color photographic light-sensitive material, which has good photographic performance, small fluctuation, and is simple.

(Prior Art) In the processing of silver halide color photographic light-sensitive materials, in order to provide a photographic image having stable and good photographic performance in recent years, the photographic performance obtained by the processing is improved by continuous processing. It is strongly desired to maintain the condition. As a problem in obtaining stable and good photographic performance, it is necessary to solve the following two problems. The first problem is that the components of the photographic processing solution are reduced by air oxidation, thermal decomposition, etc., so that the performance of the photographic processing solution is degraded. The second problem is that in continuous processing with an automatic processor, the photographic processing solution becomes thicker due to evaporation, which changes the performance of the photographic processing solution and causes the components of the photographic processing solution to precipitate, causing problems. is there.

In the color developing solution, a preservative has been studied for the former one of the above two problems, that is, for the oxidation and decomposition of the color developing agent. As these preservatives, many compounds are described in JP-A-62-215272. Among them, hydroxylamines (excluding hydroxylamine), hydroxamic acids, hydrazines, hydrazides, phenols, α- Hydroxyketones, α-aminoketones, saccharides, monoamines, diamines, polyamines, quaternary ammonium salts, nitroxy radicals, alcohols, oximes, diamide compounds, condensed amines are particularly effective. It is an organic preservative. This is Japanese Patent Application Nos. 61-147823, 61-173595, 61-165621.
No. 61-188619, No. 61-197760, No. 61-186561,
61-198987, 61-201861, 61-186559, 61-
170756, 61-188742, 61-188741, U.S. Patent No. 36
15503, 2494903, JP-A-52-143020, JP-B-48-30
No. 496, etc.

The above organic preservatives such as hydroxylamines (excluding hydroxylamine) were able to greatly suppress the reduction in deterioration of the color developing agent compared to the case where hydroxylamine or sulfite was used as the preservative. But
Further, in order to stabilize the treatment, it is necessary to take measures against evaporation.

(Problems to be Solved by the Invention) Therefore, a first object of the present invention is to provide a method for processing a silver halide color photographic light-sensitive material which can obtain good photographic properties in continuous processing and can stably obtain its performance. To provide.

It is a second object of the present invention to provide a simple processing method for maintaining good photographic properties.

(Means for Solving Problems) The present invention has been achieved by the following method.

That is, in a method of continuously processing an imagewise exposed silver halide color photographic light-sensitive material by using an automatic processor, while adding water or a washing substitute stabilizer replenisher to the color developing bath of the automatic processor. The silver halide color photographic light-sensitive material is characterized in that the color developer contains an organic preservative and the replenishing amount of the color developer is 20 to 600 ml per 1 m ^{2 of the} light-sensitive material. It was achieved by the processing method of.

In other words, it seems necessary to take measures against evaporation in order to stabilize the processing as described above.First, we examined the processing while adding water or a washing-stabilizing alternative stabilizing solution. In particular, it is difficult to control the concentration of preservatives such as hydroxylamine which has been conventionally used, and it is possible that the inventors of the present invention cause variations in photographic properties due to differences in processing amount during continuous processing and differences in water addition amount. Research revealed. However, by using the organic preservative described in the present invention, it has been found that the fluctuation of the photographic performance due to the difference in the processing amount as described above is remarkably suppressed, and the small amount processing which seems to be required to be corrected by evaporation. It can be said that the present invention, which enables low replenishment processing, is significant.

When water is added to the color developing solution in the present invention, if a wash water replenisher or a wash substitute stabilizer replenisher is used, it is not necessary to provide a new tank or pipe for replenishing water for evaporation, It is convenient. Further, when a washing water replenisher or a washing substitute stabilizer is added to the color developing solution, the replenishing amount of the washing water replenisher or washing substitute stabilizer replenisher in the washing bath or washing substitute stabilizer is the smaller the amount of the replenisher used. This is particularly preferable in a small automatic processor in which the replenisher tank and the processing unit are integrated.

The amount of water added to the color developing solution is preferably 0.1 to 1.2 times the amount of evaporation in the color developing bath in an automatic developing machine, but if it is 0.3 to 0.9 times, preferable results can be obtained regardless of the frequency of water addition. The frequency of water addition may be about once a week, but water addition once or more times a day is particularly preferable. In addition, when the automatic processor is stopped (holiday), stopped (for example, at night),
It is particularly preferable that the amount of evaporation in each period of time is examined and water is added in an amount commensurate with the amount of evaporation during each operation.

Further, it is preferable that the amount of evaporation in the automatic processor is small, since it is easy to avoid dilution due to excess water even when the automatic processor is used under various environmental conditions. As a method for reducing the amount of evaporation in the automatic processor, the opening area of the automatic processor is preferably 0.05 or less. The opening area referred to here is a value obtained by dividing the area of the liquid surface of the processing liquid (area in contact with air) (cm ² ) by the amount (ml) of the processing liquid in the processing tank.
In the processing of color photographic paper, the developer used in the present invention contains an organic-containing preservative in place of the hydroxylamine or sulfite ion, that is, does not contain hydroxylamine, and the organic preservation described in the present invention is contained. Although a remarkable effect can be obtained by using a preservative, a sufficient effect can be obtained by using an organic preservative in combination with hydroxylamine in a photographic light-sensitive material.

Here, the organic preservative refers to all organic compounds that reduce the deterioration rate of the aromatic primary amine color developing agent by being added to the processing solution of the color photographic light-sensitive material. That is, it is an organic compound having a function of preventing oxidation of a color developing agent due to air, etc. Among them, hydroxylamines (excluding hydroxylamine), hydroxamic acids, hydrazines, hydrazides, phenols, α-hydroxyl Particularly effective organic compounds include ketones, α-aminoketones, saccharides, monoamines, diamines, polyamines, quaternary ammonium salts, nitroxy radicals, alcohols, oximes, diamide compounds, and condensed amines. It is a preservative. These are Japanese Patent Application No. Sho 61-147823,
61-173595, 61-165621, 61-188619, 61-
197760, 61-186561, 61-198987, 61-20186
No. 1, 61-186559, 61-170756, 61-188742,
No. 61-188741, U.S. Pat.No. 3615503, No. 2494903,
It is disclosed in JP-A-52-143020, JP-B-48-30496, and the like.

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 do not become hydrogen atoms at the same time and may be linked to each other to form a heterocycle together with a nitrogen atom.

The heterocyclic ring structure is a 5- or 6-membered ring, and is composed of carbon atoms, hydrogen atoms, halogen atoms, nitrogen atoms, sulfur atoms and the like, and may be saturated or unsaturated.

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.

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 carbon number is preferably 10 or less.

X ²¹ -SO ₂ -, or represents a -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 ¹ , R ² and R ³ each independently represent a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, and R ⁴ is a hydrogen atom, a hydroxy group, a hydrazino group, an alkyl group, an aryl group or a heterocyclic group. Group, alkoxy group, aryloxy group,
It represents a carbamoyl group or an amino group, X ¹ represents a divalent group, and n represents 0 or 1. However, when n = 0, R ⁴ represents an alkyl group, an aryl group or a heterocyclic group. R ³ and
R ⁴ may together form a heterocycle.

The hydrazine analogues (hydrazines and hydrazides) represented by the general formula (III) in the present invention will be described in detail below.

R ¹ , R ² and R ³ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group (preferably having a carbon number of 1 to 20, for example, methyl group, ethyl group, sulfopropyl group, carboxybutyl group, hydroxyethyl group, Cyclohexyl group, benzyl group, phenethyl group, etc., substituted or unsubstituted aryl group (preferably having 6 to 20 carbon atoms, for example, phenyl group, 2,5-dimethoxyphenyl group, 4-hydroxyphenyl group, 2-carboxyphenyl group) Etc.) or a substituted or unsubstituted heterocyclic group (preferably having 1 to 20 carbon atoms,
It is preferably a 5- or 6-membered ring, and oxygen as a hetero atom,
Those containing at least one of nitrogen, sulfur and the like, for example, pyridin-4-yl group, N-acetylpiperidine-4
-Yl group).

R ⁴ is a hydrogen atom, a hydroxy group, a substituted or unsubstituted hydrazino group (for example, a hydrazino group, a methylhydrazino group, a phenylhydrazino group, etc.), a substituted or unsubstituted alkyl group (preferably having 1 to 20 carbon atoms, for example, Methyl group, ethyl group, sulfopropyl group, carboxybutyl group, hydroxyethyl group, cyclohexyl group, benzyl group, t-butyl group, n-octyl group, etc., substituted or unsubstituted aryl group (preferably having 6 to 6 carbon atoms). 20, for example, phenyl group, 2,5-dimethoxyphenyl group, 4-hydroxyphenyl group, 2-carboxyphenyl group, 4-sulfophenyl group, etc., substituted or unsubstituted heterocyclic group (preferably having 1 to 20 carbon atoms) Preferably, it is a 5- or 6-membered ring and contains at least one of oxygen, nitrogen and sulfur as a hetero atom. For example, pyridin-4-yl group, imidazolyl group, etc., substituted or unsubstituted alkoxy group (preferably having 1 to 20 carbon atoms, for example, methoxy group, ethoxy group, methoxyethoxy group, benzyloxy group, cyclohexyloxy group, octyloxy group) Such),
A substituted or unsubstituted aryloxy group (preferably having a carbon number of 6 to 20, for example, phenoxy group, p-methoxyphenoxy group, p-carboxyphenyl group, p-sulfophenoxy group, etc.), substituted or unsubstituted carbamoyl group (preferably 1 to 20 carbon atoms, for example, an unsubstituted carbamoyl group,
N, N-diethylcarbamoyl group, phenylcarbonyl group, etc.) or substituted or unsubstituted amino group (preferably having 0 to 20 carbon atoms, for example, amino group, hydroxyamino group, methylamino group, hexylamino group, methoxyethylamino group) , Carboxyethylamino group, sulfoethylamino group, N-phenylamino group, p-sulfophenylamino group).

Further substituents for R ¹ , R ² , R ³ and R ⁴ include a halogen atom (chlorine, bromine, etc.), a hydroxy group, a carboxy group,
Sulfo group, amino group, alkoxy group, amide group, sulfonamide group, carbamoyl group, sulfamoyl group, alkyl group, aryl group, aryloxy group, alkylthio group, arylthio group, nitro group, cyano group, sulfonyl group, sulfinyl group, etc. Are preferred, and they may be further substituted.

X ¹ is preferably a divalent organic residue, and specifically,
For example, -CO-, -SO-, and Represents n = 0 or 1. However, when n = 0, it represents a group selected from R ⁴ , a substituted or unsubstituted alkyl group, an aryl group, a heterocyclic group and a heterocyclic group. R ¹ and R ² and R ³ and R ⁴ may together form a heterocyclic group. When n is 0, at least one of R ^{1 to} R ⁴ is preferably a substituted or unsubstituted alkyl group, and particularly R ¹ , R ² , R ³ and R ⁴ are hydrogen atoms, or a substituted or unsubstituted alkyl group. A group is preferred. (However, R ¹ , R ² ,
R ³ and R ⁴ are never hydrogen atoms at the same time. In particular, when R ¹ , R ² and R ³ are hydrogen atoms and R ⁴ is a substituted or unsubstituted alkyl group, R ¹ and R ³ are hydrogen atoms and R ² and R ⁴ are When it is a substituted or unsubstituted alkyl group, or R ¹ and R ² are hydrogen atoms, and R ³ and R ⁴
Is preferably a substituted or unsubstituted alkyl group (at this time, R ³ and R ⁴ may together form a heterocycle). When n = 1, X ¹ is preferably -CO-,
R ⁴ is preferably a substituted or unsubstituted amino group,
R ^{1 to} R ³ are preferably a hydrogen atom or a substituted or unsubstituted alkyl group.

As n, 0 is more preferable.

The alkyl group represented by R ^{1 to} R ⁴ preferably has 1 to 10 carbon atoms, and more preferably 1 to 7 carbon atoms. In addition, examples of preferable substituents on the alkyl group include a hydroxyl group, a carboxylic acid group, a sulfonic acid group and a phosphonic acid group. When there are two or more substituents, they may be the same or different.

The compound of the general formula (III) may form a bis body, a tris body or a polymer linked by R ¹ , R ² , R ³ and R ⁴ .

Specific examples of the compound represented by the general formula (III) are shown below, but the invention is not limited thereto.

(III-2) CH ₃ NHNHCH ₃ (III-8) HOOCCH ₂ NHNHCH ₂ COOH (III-9) NH ₂ NHCH _{2 3} NHNH ₂ (III-10) NH ₂ NHCH ₂ CH ₂ OH (III-12) NH ₂ NH- (CH ₂ ) ₃ -SO ₃ H (III-13) NH ₂ NH- (CH ₂ ) ₄ -SO ₃ H (III-14) NH ₂ NH- (CH ₂ ) ₃ -COOH (III-19) NH ₂ NHCH ₂ CH ₂ COONa (III-20) NH ₂ NHCH ₂ COONa (III-21) H ₂ NNHCH ₂ CH ₂ SO ₃ Na (III-25) H2NNCH ₂ CH ₂ SO ₃ Na) ₂ (III-26) H ₂ NNCH ₂ CH ₂ CH ₂ SO ₃ Na) ₂ (III-34) NH ₂ NHCONH ₂ (III-36) NH ₂ NHCONHNH ₂ (III-37) NH ₂ NHSO ₃ H (III-38) NH ₂ NHSO ₂ NHNH ₂ (III-39) CH ₃ NHNHSO ₂ NHNHCH ₃ (III-40) NH ₂ NHCONH- (CH ₂ ) ₃ -NHCONHNH ₂ (III-42) NH ₂ NHCOCONHNH ₂ (III-46) NH ₂ COCONHNH ₂ (III-63) NH ₂ NHCOOC ₂ H ₅ (III−64) NH ₂ NHCOCH ₃ (III-67) NH ₂ NHCH ₂ PO ₃ H ₂ (III-73) (CH ₃ ) ₃ CCONHNH ₂ (III-80) HOCH ₂ CH ₂ SO ₂ NHNH ₂ (III-81) NaO ₃ SCH ₂ CH ₂ CONHNH ₂ (III-82) H ₂ NCONHCH ₂ CH ₂ SO ₂ NHNH ₂ (III-85) H ₂ NNHCH ₂ CH ₂ PO ₃ H ₂ As a specific example other than the above, Japanese Patent Application No. 61-170756, specification 11
Pp.-24, 61-171682, pp. 12-22, 61-1734.
Examples of the compounds described on pages 9 to 19 of the specification No. 68 can be given.

Many of the compounds represented by the general formula (III) are available as commercial products, and "Organic Syntheses", Coll. Vol. 2, pp208-213;
Jour.Amer.Chem.Soc, 36, 1747 (1914) ;. Oil Chemistry, 24, 31
(1975); Jour. Org. Chem. 25 , 44 (1960); Pharmaceutical Journal, 9
1 , 1127 (1971); "Organic Synthesis" (Orga
nic Syntheses), Coll. Vol. 1, p450; "New Experimental Chemistry Lecture", Volume 14, III, p1621-1628 (Maruzen); Beil., 2 , 5,559; Bei
l., 3 , 117; EB Mohr et al., Inorg.Syn., 4 , 32 (1953);
FJ Willson, ECPickering, J. Chem. Soc., 123 , 394 (192
3); NJ Leonard, JH Boyer, J. Org. Chem. 15 , 42 (195
0); "Organic Synthes"
es), Coll. Vol.5, p 1055; PASSmith, `` Derivatives o
f hydrazine and other hydronitrogens having nn−bo
nds '', p120-124, p130-131; THE BENJAMIN / CUMMINGS CO
MPANY. (1983); Staniey R. Sandier Waif Karo. "Organ
ic Functional Group Preparations '', Vol.1, Second Ed
It can be synthesized according to a general formula synthesis method such as ition, p457.

The following are preferred as 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, their types 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. The ring structure is a 5- or 6-membered ring, which 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 in the ortho position or the rose 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 rose position.

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 carbon ring or a chlorine ring. R ⁵³ 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 . Monosaccharides are generally aldehydes or ketones of polyhydric alcohols (called aldose and ketose, respectively) and their reduced derivatives,
It is a generic term for 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.

VI-1 D-oxylose VI-2 L-arabinose VI-3 D-ribose VI-4 D-deoxyribose VI-5 D-glycose VI-6 D-galactose VI-7 D-mannose VI-8 Glucosamine VI-9 L-sorbose VI-10 D-sorbit (sorbitol) Examples of monoamines include the following.

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. Further, examples of the substituent include a hydroxyl group, a sulfone group, a carboxyl group, a halogen atom, a nitro group, an amino group and the like.

VII-1 NCH ₂ CH ₂ OH) ₃ VII-2 H ₂ NCH ₂ CH ₂ OH VII-3 HNCH 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 represent a hydrogen atom, an alkyl group, 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 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. The organic group here is carbon
Represents a group of 1 or more, specifically, an alkyl group or an aryl group
And a heterocyclic group. R¹⁰², R¹⁰³And R¹⁰⁴Nou
A quaternary ammonium source in which at least two groups are bonded
A heterocycle containing a child may be formed. n is an integer of 1 or more
Yes, 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 , R ¹³² , and R ¹³³ each represent a hydrogen atom or an alkyl 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 ₃ 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 Approx. 300 XIII-8 HOCH ₂ CH ₂ O _n H Average molecular weight Approx. the following are preferred as _{800 XIII-9 HOCH 2 CH 2} O n H average molecular weight of about _{3000 XIII-10 HOCH 2 CH 2} O n H average molecular weight of about 8000 oximes.

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. R ¹⁴¹ and R ¹⁴² may be the same or different, and these groups may be linked together.

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 preferable polyamines.

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.

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 (I
X) and 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 (X).

In general formula (1-b), it is preferable that R ¹ and R ² have 6 or less carbon atoms. R ¹ and R ² are preferably an alkyl 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 formula (XV) according to the present invention can be easily obtained as commercial products.

In addition, it can be synthesized according to the following documents.

・ Khim.Geterotsikl.Soedin., (2), 272-5 (1976) ・ USUS 3297701,10 Jan 1967,6pp. ・ USUS 3375252,26 Mar 1968,2pp. ・ Khim.Geterotsikl.Soedin., (8), 1123 ~ 6 (167
6).・ USUS 4092316, 30 May 1978, 7 pp. Etc. The above organic preservatives may be used in combination of two or more kinds. A preferred combination is at least one compound of the general formulas (I) to (VI) and at least one compound of (VII) to (XVI).

More preferable combined use is at least one of the general formulas (I) and (III) and at least one of the general formulas (VII) and (XVI).

Most preferably, at least one of the general formula (I) and at least one of the general formula (VII) are used in combination.

Next, each step will be described.

Color Development The color developer 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 2-amino-5-diethylaminotoluene D-3 2-amino-5- (N-ethyl-N-laurylamino) toluene D-4 4- [ N-ethyl-N- (β-hydroxyethyl) amino] aniline D-5 2-methyl-4- [N-ethyl-N- (β-hydroxyethyl) amino] aniline D-6 4-amino-3-methyl -N-ethyl-N-
[Β- (Methanesulfonamido) ethyl] -aniline D-7 N- (2-amino-5-diethylaminophenylethyl) methanesulfonamide D-8 N, N-dimethyl-p-phenylenediamine D-9 4-amino -3-Methyl-N-ethyl-N-methoxyethylaniline D-10 4-amino-3-methyl-N-ethyl-N-β
-Ethoxyethylaniline D-11 4-amino-3-methyl-N-ethyl-N-β
-Butoxyethylaniline Further, these p-phenylenediamine derivatives may be salts such as sulfates, hydrochlorides, sulfites and p-toluenesulfonates. The amount of the aromatic primary amine developing agent used is preferably about 0.1 g to about 20 g, more preferably about 0.5 g to about 10 g per developer.

Further, as a preservative, a sulfite salt such as sodium sulfite, potassium sulfite, sodium bisulfite, potassium bisulfite, sodium metasulfite, potassium metasulfite, or a carbonyl sulfite adduct is added to the color developer as needed. be able to. However, in order to improve the color developability of the color developer, it is preferable that the amount of sulfite ion added is small.

Specifically, it is 0 to 0.01 mol, preferably 0 to 0.005 mol, and most preferably 0 to 0.002 mol, per 1 color developing solution. The smaller the amount of sodium sulfite added, the smaller the change in photographic characteristics during the small amount treatment, and the more preferable.

For the above-mentioned reason, the addition amount of hydroxylamine conventionally used as a preservative is preferably small, and specifically, 0 to 0.02 mol, more preferably 0 to 0.01 mol, and most preferably 1 mol of color developing solution. Is 0 to 0.005 mol.

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, carbonate, phosphate, borate, tetraborate, hydroxybenzoate, glycyl salt,
N, N-dimethylglycine salt, leucine salt, norleucine salt, guanine salt, 3,4-dihydroxyphenylalanine salt, alanine salt, aminobutyrate, 2-amino-2-methyl-1,3-propanediol salt, valine salt , Proline salt, trishydroxyaminomethane salt, lysine salt and the like can be used. In particular, carbonates, phosphates, tetraborate and hydroxybenzoates are highly soluble and have a high pH of 9.0 or above.
It is particularly preferable to use these buffers because they have excellent buffering ability in the H region, have no adverse effect on photographic performance (fog, etc.) even when added to a color developing solution, and are inexpensive.

Specific examples of these buffers include sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, disodium phosphate, dipotassium phosphate, sodium borate, boric acid. Potassium, sodium tetraborate (borax), potassium tetraborate, sodium o-hydroxybenzoate (sodium salicylate), potassium o-hydroxybenzoate, sodium 5-sulfo-2-hydroxybenzoate (5-sulfoxalicylic acid) Sodium), potassium 5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate)
And so on. However, the present invention is not limited to these compounds.

The amount of the buffer added to the color developing solution is preferably 0.01 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.

As the chelating agent, organic acid compounds are preferable, for example, aminopolycarboxylic acids described in JP-B-48-30496 and 44-30232, JP-A-56-97347, JP-B-56-39359, and West German Patent No. 2,227,639. Organic phosphonic acids described, JP-A-5
2-102726, 53-42730, 54-121127, 55-1262
Examples thereof include phosphonocarboxylic acids described in JP-A Nos. 41 and 55-659509, and other compounds described in JP-A Nos. 58-195845, 58-203440 and 53-40900.
Specific examples are shown below, but the present invention is not limited thereto.

Nitrilotriacetic acid, diethylenetriaminepentaacetic acid, ethylenediaminetetraacetic acid, N, N, N-trimethylenephosphonic acid,
Ethylenediamine-N, N, N ', N'-tetramethylenephosphonic acid, transcyclohexanediaminetetraacetic acid, 1,2
-Diaminopropane tetraacetic acid, glycol ether diamine tetraacetic acid, ethylenediamine orthohydroxyphenylacetic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid,
1-hydroxyethylidene-1,1-diphosphonic acid, N, N '
-Bis (2-hydroxybenzyl) ethylenediamine-
N, N'-diacetic acid These chelating agents may be used in combination of two or more, if necessary.

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. However, it is preferable that the color developing solution of the present invention does not substantially contain benzyl alcohol from the viewpoints of pollution, solution preparation and color contamination prevention. Here, “substantially” means that the amount of the developer is not more than 2 ml, preferably not contained at all.

The above-mentioned organic preservative used in the present invention has a remarkable effect in the processing step using a color developer containing substantially no benzyl alcohol.

Other development accelerators include JP-B-37-16088 and 37-5
No. 987, No. 38-7826, No. 44-12380, No. 45-9019, and thioether compounds represented in U.S. Pat.No. 3,813,247, etc., represented by JP-A Nos. 52-49829 and 50-15554. p-Phenylenediamine compound, JP-A-50-137726
JP-B-44-30074, JP-A-56-156826 and 52-43
429, etc., quaternary ammonium salts, US Pat. Nos. 2,494,903, 3,128,182, 4,230,796, and
3,253,919, Japanese Patent Publication No. 41-11431, U.S. Pat.No. 2,482,546
Nos. 2,596,926 and 3,582,346, etc., amine compounds, JP-B-37-16088, JP-B-42-25201, U.S. Pat.No. 3,128,183, JP-B-41-11431, 42-23883 and US If necessary, polyalkylene oxide represented by Japanese Patent No. 3,532,501 and the like, 1-phenyl-3-pyrazolidones, imidazoles and the like can be added.

In the present invention, any antifoggant 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 developing solution 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 g 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 2 minutes, preferably 30 seconds to 1 minute. The amount of replenishment is preferably as small as possible, but it is ^{20 to} 600 ml, preferably 30 to 300 ml per 1 m ^{2 of} the light-sensitive material. More preferably, it is 30 ml to 120 ml.

Bleach-fixing solution As the bleaching agent used in the bleach-fixing solution of the present invention, any bleaching agent can be used, but especially an organic complex salt of iron (III) (for example, ethylenediaminetetraacetic acid,
Aminopolycarboxylic acids such as diethylenetriaminepentaacetic acid, complex salts such as aminopolyphosphonic acid, phosphonocarboxylic acid and organic phosphonic acid) or organic acids such as citric acid, tartaric acid, malic acid; preferable.

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: ethylenediaminetetraacetic acid, diethyleneditriaminepentaacetic acid, 1,3- Examples thereof include diaminopropanetetraacetic acid, propylenediaminetetraacetic acid, nitrilotriacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, iminodiacetic acid and glycol etherdiaminetetraacetic acid.

These compounds may be sodium, potassium, lithium or ammonium salts. Among these compounds, the iron (III) complex salts of ethylenediaminetetraacetic acid, 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. Various compounds can be used as a bleaching accelerator in the bleaching solution, the bleach-fixing solution and / or the pre-bath thereof. For example, U.S. Pat.No. 3,893,858, German Patent No. 1,290,812, and Japanese Patent Laid-Open No. 53-95630.
Publication, Research Disclosure No. 17129 (1978
July 1989), compounds having a mercapto group or a disulfide bond, JP-B-45-8506, and JP-A-52-2083.
No. 2, No. 53-32735, U.S. Pat. No. 3,706,561 and the like, and thiourea compounds or halides such as iodine and bromine ions are preferable because of their excellent bleaching power.

In addition, the bleach-fixing solution used in the present invention contains a rehalogenating agent such as bromide (eg, potassium bromide, sodium bromide, ammonium bromide) or chloride (eg, potassium chloride, sodium chloride, ammonium chloride). Can be included. Boric acid, borax, sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, phosphorous acid, phosphoric acid, sodium phosphate, citric acid, if necessary.
Has a pH buffering capacity for sodium citrate, tartaric acid, etc. 1
It is possible to add more than one kind of inorganic acid, organic acid and their alkali metal or ammonium salts, 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. Also,
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 also be used. In the present invention, it is preferable to use thiosulfate, particularly ammonium thiosulfate. The amount of the fixing agent per used liquid is 0.3 to 3
Molar is preferable, and more preferably 0.5 to 2.0 mol. The pH range of the bleach-fixing solution or the fixing solution is preferably 3-10, and more preferably 5-9.

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

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

As a preservative, it is common to add sulfite, but in addition, ascorbic acid and carbonyl bisulfite adduct,
Alternatively, 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 if necessary.

In the bleach-fixing solution of the present invention, a part or all of the overflow of the washing and / or stabilizing solution which is a post-bath is introduced. This amount is 10 ml to 500 ml per 1 m ² of the light-sensitive material, preferably 2
0 ml to 300 ml, most preferably about 30 ml to 200 ml.

If the amount of the washing and / or stabilizing solution to be introduced is small, the effect of cost reduction and waste solution amount reduction is small, and if too large, the bleach-fixing solution is diluted to cause desilvering failure.

The bleach-fixing replenisher of the present invention preferably has a concentration as high as possible for the purpose of reducing the amount of waste liquid, and the concentration of the bleaching agent is 0.15 to 0.40 mol /
l is optimal, and the concentration of the fixing agent is optimally 0.5 to 2.0 mol / l.

The replenishing amount of the bleach-fixing replenisher is 30 ml to 200 m per 1 m ² of the light-sensitive material.
More preferably, it is 40 ml to 100 ml. The bleach-fixing replenisher may be replenished by separating the bleaching agent and the fixing agent.

The processing temperature in the bleach-fixing step of the present invention is 20 ° to 50 ° C, preferably 30 ° to 40 ° C. The processing time is preferably 20 seconds to 2 minutes
30 seconds to 1 minute.

Water Washing Step and / or Stabilizing Step Next, the water washing step and the stabilizing step in the present invention will be described in detail. The replenishing amount in the washing or stabilizing process is 1 to 50 times the amount brought from the previous bath per unit area of the light-sensitive material to be processed.
The capacity is twice, preferably 2 to 30 times, particularly preferably 3 times.
~ 20 times.

The replenishment amount in the washing and / or stabilizing step can be set within a wide range depending on various characteristics such as characteristics of the light-sensitive material (for example, coupler), application, temperature, countercurrent, cocurrent, and the like. Of these, the relationship between the number of washing tanks and the amount of water in the multi-stage countercurrent system is described in the Journal of the Society of Motion Pixar and Television.
Engineers (Journal of the Society of Motion Pic
ture and Television Engineers) Volume 64, p.248-253
It can be obtained by the method described in (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.

Therefore, the preferable amount of replenishment per 1 m ^{2 of} light-sensitive material is 300 ml to 1000 ml in the case of the two-tank countercurrent method and 1 in the case of the three-tank countercurrent method
00ml-500ml, 100ml-500ml in case of 3 tank counter-current method,
In the case of 4-tank counter-current method, it will be about 50ml-300ml. or,
The amount of the pre-bath component brought in is about ^{20 to} 60 ml per 1 m ² of the light-sensitive material.

Various compounds can be added to the washing water of the present invention. For example, isothiazolone compounds and siabendazoles described in JP-A-57-8542, chlorinated germicides such as chlorinated sodium isocyanurate described in JP-A-61-120145, and Japanese Patent Application No. 60-105487. Benzotriazole,
Copper ion, etc. Hiroshi Horiguchi, “Chemistry of antibacterial and antifungal agents”, Hygiene Technology Society, “Microbial sterilization, sterilization, antifungal technology”, Japan Antibacterial and Antifungal Society, “Encyclopedia of antibacterial and antifungal agents” The disinfectants described can also be used.

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. In addition, in order to prevent the growth of bacteria in the liquid and to impart antifungal properties to the processed light-sensitive material, the antifungal properties of the above-mentioned various bactericides can be used.

Further, a surfactant, an optical brightener and a hardener may 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, it is disclosed in JP-A-57-8.
All known methods described in No. 543, 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.

The water washing step in the present invention may be called a rinse step.

In the washing step and / or stabilizing step of the present invention, the concentration of calcium and magnesium in the replenisher is 4 mg / l.
It is preferable to reduce the amount to the following.

That is, by reducing the amount of calcium and magnesium in the replenisher, the amount of calcium and magnesium in the washing tank and the stabilizing tank is inevitably lowered, which makes it possible to prevent mold and fungus without the use of bactericides and fungicides. Bacterial growth is prevented,
In addition, dirt and deposits on the conveying roller and squeeze blade of the automatic processor can be eliminated at the same time.

In the present invention, calcium and magnesium in the replenisher for the washing step and / or the stabilizing step (hereinafter referred to as the washing replenisher or the stable replenisher) are preferably 5 mg / l or less as described above, and more preferably 3 mg / l. It is 1 or less, particularly preferably 1 mg / l or less.

Although various known methods can be used to adjust the concentrations of calcium and magnesium in the water washing or stable replenisher as described above, it is preferable to use an ion exchange resin and / or a reverse osmosis device.

Although various cation exchange resins can be used as the above-mentioned ion exchange resin, it is preferable to use a Na-type cation exchange resin in which Ca and Mg are replaced with Na.

An H type cation exchange resin can also be used, but in this case the pH of the treated water becomes acidic, so it is preferable to use it with an OH type anion exchange resin.

The ion exchange resin is preferably a strongly acidic cation exchange resin having a styrene-divinylbenzene copolymer as a base and having a sulfone group as an ion exchange group. Examples of such an ion exchange resin include DIA Kay SK-1B and DIAION PK-216 manufactured by Mitsubishi Kasei Co., Ltd. It is preferable that the base of these ion exchange resins has a charged amount of divinylbenzene of 4 to 16% with respect to the charged amount of all monomers at the time of production. As the anion exchange resin which can be used in combination with the H type cation exchange resin, a strongly basic anion exchange resin having a styrene-divinylbenzene copolymer as a base and having a tertiary amine or a quaternary ammonium group as an exchange group is preferable. . Examples of such anion exchange resin include, for example, DIAION SA-10A or DIAION PA-418, which are also trade names of Mitsubishi Kasei Co., Ltd.

Further, in the present invention, a reverse osmosis treatment machine may be used for the purpose of reducing the replenishment amount of the washing water and / or the stabilizing solution.

As the reverse osmosis treatment device used in the present invention, a known device can be used without limitation, but the area of the reverse osmosis membrane is 3 m ²
Hereinafter, it is desirable to use an ultra-compact device having a working pressure of 30 kg / m ² or less, particularly preferably 2 m ² or less, and 20 kg / m ² or less. When such a small device is used, workability is good and sufficient water saving effect can be obtained. Furthermore, activated carbon or a magnetic field can be passed through.

As the reverse osmosis membrane of the reverse osmosis treatment apparatus, acetic acid, cellulose acetate membrane, ethyl cellulose / polyacrylic acid membrane, polyacrylonitrile membrane, polyvinylene carbonate membrane, polyether sulfonic acid, etc. can be used.

Further, the liquid feed pressure is usually 5~60kg / cm ² is used but to achieve the object of the present invention is sufficient 30kg / cm ² or less, 10
What is called a low-pressure reverse osmosis device of kg / cm ² or less can be sufficiently used.As the structure of the reverse osmosis membrane, any of spiral type, tubular type, hollow fiber type, pleated type and rod type can be used. it can.

Further, in the present invention, the liquid in at least one tank selected from a washing tank or a stabilizing tank and its replenishing tank may be irradiated with ultraviolet rays, which makes it possible to further suppress the growth of mold.

As the ultraviolet lamp used in the present invention, a low pressure mercury vapor discharge tube emitting a line spectrum having a wavelength of 253.7 nm is used. In the present invention, those having a germicidal ray output of 0.5 W to 7.5 W are particularly preferably used.

The ultraviolet lamp may be installed by irradiating by arranging it outside the liquid, or may be installed by irradiating in the liquid and irradiating from inside the liquid.

According to the present invention, the sterilizing agent and the antibacterial agent may not be contained in the water washing and / or the stable replenishing solution, but they can be optionally used if their use does not affect the performance of the prebath.

The pH of the washing or stabilizing solution is usually 4-9, preferably 5-8. However, depending on the application and purpose, an acidic (pH 4 or less) stabilizing solution containing acetic acid may be used.

Next, the time for washing or stabilizing treatment will be described.

The washing or stabilizing treatment in the present invention is carried out for 10 seconds to 4 minutes, but a shorter time is preferable from the viewpoint that the effects of the present invention can be more exerted.
Seconds to 3 minutes, particularly preferably 20 seconds to 2 minutes.

It is preferable to combine various washing promoting means in the washing or stabilizing step. As such accelerating means, ultrasonic oscillation in liquid, air bubbling, jet impingement on the surface of the photosensitive material, compression by a roller and the like can be used. The temperature of the washing or stabilizing step is in the range of 20 to 50 ° C, preferably 25 to 45 ° C, more preferably 30 to 40 ° C.

The overflow in the washing and / or stabilizing step refers to the liquid overflowing outside the tank as it is replenished, but various methods can be adopted to introduce this overflow into the prebath. For example,
A method may be used in which a slit is put in the upper part of the phosphorus wall with the pre-bath in the automatic processor to allow an overflow to flow in, or once stored outside the automatic processor and then supplied using a pump.

Thus, by introducing the overflow into the pre-bath, by adding a small volume of a more concentrated replenisher to the pre-bath, it is possible to maintain the components in the bath at the required concentration,
As a result, the volume of waste liquid can be reduced by the amount of thickening of the prebath replenisher.

Of course, the same effect can be obtained by storing the overflow in the liquid preparation tank, adding the replenishing liquid component to this, and finishing the replenishing liquid for use.

In addition, since the prebath component is contained in the overflow due to being brought in, the absolute amount of the component replenished in the prebath can be reduced by using this, reducing the pollution load and the treatment cost. Can be planned.

The amount of overflow introduced into the pre-bath can be arbitrarily set so as to conveniently control the concentration of the pre-bath, but normally, the ratio of the mixing amount of the overflow liquid to the replenishing amount of the pre-bath is set to 0.2 to 5, It is preferably set to 0.3 to 3, particularly preferably 0.5 to 2.

In the present invention, when a wash water replenisher or a wash substitute stabilizer replenisher is added to the color developer, the wash water replenisher or wash substitute stabilizer contains ammonium ions such as ammonium chloride and ammonia water. It is preferred not to include a releasing compound. This is to prevent deterioration of photographic properties.

Next, specific processing steps of the present invention are shown below, but the steps of the present invention are not limited to these.

1. Color development-bleaching- (washing with water) -bleach-fixing- (washing with water)-
(Stable) 2. Color development-bleach fixing- (washing)-(stable) 3. Color development-bleaching-bleaching fixing- (washing)-(stable) 4. Color developing-bleaching fixing-bleaching fixing- (washing) -(Stable) 5. Color development-Bleaching-Fixing-Bleach fixing- (Washing)-(Stable) 6. Black-and-white development-Water washing- (Reverse) -Color development- (Adjustment) -Bleaching-Bleach fixing- (Washing)- (Stable) 7. Black and white development-water washing- (reversal) -color development- (adjustment) -bleach fixing- (water washing)-(stable) 8. Black-and-white development-water wash- (reversal) -color development- (adjustment) -bleaching -Bleach-fixing- (washing with water) 9. Color development-fixing-bleach-fixing- (washing with water) 10. Color-developing-fixing-bleach-fixing-bleach-fixing- (washing) The steps marked with () above are the types of sensitive materials. Although it can be omitted depending on the purpose and application, washing with water and stability cannot be omitted at the same time. Further, the washing process may be replaced with a stabilizing process.

The method of the present invention can be applied to any processing step. For example, it can be applied to reversal of color paper, color reversal paper, color direct positive light-sensitive material, color positive film, color negative film, color reversal film, etc., but it is particularly preferably applied to color paper and color reversal paper.

Next, the silver halide color photographic light-sensitive material processed in the present invention will be described in detail.

It is necessary that the light-sensitive material processed in the present invention contains various color couplers. 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 shea, magenta and yellow couplers that can be used in the present invention are Research Disclosure (RD) 17643 (December 1978), Section VII-D and the same.
18717 (November 1979).

The color coupler incorporated in the light-sensitive material preferably has a ballast group or is polymerized to be diffusion resistant. A two-equivalent color coupler in which a coupling active position is substituted with a leaving group is preferable to a four-equivalent color coupler having a hydrogen atom, because the amount of coated silver can be reduced and the effect of the present invention is large. A coupler in which the color-forming dye has a suitable diffusibility, a colorless coupler, or a DIR coupler which releases a development inhibitor upon coupling reaction or a coupler which releases a development accelerator can also be used.

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-58-10739, U.S. Patent No. 4,401,752, No. 4,326,0
24, 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, especially the light fastness, while
The benzoylacetanilide coupler provides 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. 2,600,783, 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.

Pyrazoloazole-based couplers include U.S. Pat.
No. 879 pyrazolobenzimidazoles, preferably pyrazolo [5,1−, described in US Pat. No. 3,725,067.
c] [1,2,4] triazoles, pyrazolotetrazoles described in Research Disclosure 24220 (June 1984) and Research Disclosure 24230 (1)
Pyrazolopyrazoles described in Jun. 984). 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.

Cyan couplers that can be used in the present invention include oil-protected naphthol-based and phenol-based couplers, and naphthol-based couplers described in U.S. 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. 2,895,326, etc. Cyan couplers which are fast against humidity and temperature are preferably used in the present invention, and typical examples thereof include a phenol system having an alkyl group of ethyl group or more at the meta position of the phenol nucleus described in U.S. Pat.No. 3,772,002. Cyan coupler, U.S. Pat.
3,758,308, 4,126,396, 4,334,011, 4,327,173, West German Patent Publication 3,329,729 and Japanese Patent Application No. 58-42671, and the like, 2,5-diacylamino-substituted phenol couplers and U.S. Patents. Third 3,446,622
Nos. 4,333,999, 4,451,559 and 4,42
Nos. 7,767 and the like include phenolic couplers having a phenylureido group at the 2-position and an acylamino group at the 5-position.

In the present invention, if necessary, various couplers may be used in combination, and a coupler in which the coloring dye has an appropriate diffusibility may be used in combination to improve the graininess. Such dye-diffusing couplers are described in U.S. Pat.
And British Patent No. 2,125,570 describe specific examples of magenta couplers, and European Patent No. 96,570 and published German Patent Application No. 3,234,533 describe specific examples of yellow, magenta or cyan couplers.

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 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 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 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. For example, when performing rapid processing or low replenishment processing of color paper, a silver chlorobromide emulsion or a silver chloride emulsion containing 60 mol% or more of silver chloride is preferable, and the content of silver chloride is 80 to 100. The case of mol% is particularly preferable. In addition, high sensitivity is required, and at the time of manufacturing,
When it is necessary to suppress the fog during storage and / or processing to a particularly low level, a silver chlorobromide emulsion or a silver bromide emulsion containing 50 mol% or more of silver bromide (3 mol% or less of silver iodide) May be contained), and more preferably 70 mol% or more. Silver iodobromide and silver chloroiodobromide are preferable for the color light-sensitive material for photographing, and the silver iodide content is preferably 3 to 15 mol%.

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 distribution of the silver halide grains used in the present invention may be narrow or wide, but the standard deviation value in the grain size distribution curve of the silver halide emulsion is divided 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. Furthermore, two or more kinds of polydisperse silver halide emulsions or a combination of monodisperse emulsions and polydisperse emulsions can be mixed or laminated and used.

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 an irregular crystal form such as a spherical shape, or may have a composite form of these crystal forms. Further, tabular grains may be used, and in particular, tabular grains having a length / thickness ratio value of 5 to 8 or 8 or more,
Emulsions which account for 50% or more of the total projected area of the 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 forms a latent image inside the grains.

The photographic emulsion used in the present invention is RESEARCH DISCLOSURE.
It can be adjusted using the method described in vol.170 Item No.17643 (I, II, III) (1978.12).

The emulsion used in the present invention is usually one that has been physically ripened, chemically ripened and spectrally sensitized. Additives used in such processes are Research Disclosure Vol. 176, No. 17643 (December 1979) and Vol. 187, N.
No. 18716 (November, 1979), the relevant 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.

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. . For details on the support and coating method, see RESEAR
CH DISCLOSURE Volume 176, Item 17643, Item XV (p.27) XVII
Section (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.

(Example) Hereinafter, the present invention will be described in detail based on examples.

Example 1 On a paper support laminated on both sides with polyethylene, a multi-layer photographic paper (Sample 101) having the following layer constitution was prepared.
The coating liquid was prepared as follows.

(Preparation of coating solution for the first layer) 19.2 g of yellow coupler (ExY-1) and 4.4 g of color image stabilizer (Cpd-1) were mixed with 27.2 cc of ethyl acetate and 7.7 cc (8.0 g) of high boiling solvent (Solv-1). Add and dissolve, and add this solution to 1
10% containing 8% sodium dodecylbenzene sulfonate 10
% Gelatin aqueous solution was emulsified and dispersed in 185 cc. This emulsified dispersion and emulsions EM7 and EM8 were 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. 1-Oxy-3,5-dichloro-s-triazine sodium salt was used as a gelatin hardening agent for each layer.

Moreover, (Cpd-1) 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 content (Ti02) and bluish dye. ] First layer (blue-sensitive layer) Monodisperse spectrally sensitized with sensitizing dye (ExS-1) Silver chlorobromide emulsion (EM7) 0.15 Monodisperse spectrally sensitized with sensitizing dye (ExS-1) Silver chlorobromide emulsion (EM8) 0.15 Gelatin 1.86 Yellow coupler (ExY-1) 0.82 Color image stabilizer (Cpd-2) 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) Monodisperse silver chlorobromide emulsion (EM9) spectrally sensitized with sensitizing dye (ExS-2,3) 0.12 Sensitizing dye (ExS-2,3) Dispersion-sensitized silver chlorobromide emulsion (EM10) 0.24 Gelatin 1.24 Magenta coupler (ExM-1) 0.39 Color image stabilizer (Cpd-4) 0.25 Color image stabilizer (Cpd-5) 0.12 Solvent (Solv -2) 0.25 4th layer (UV absorbing layer) Gelatin 1.60 UV absorbing agent (Cpd-6 / Cpd-7 / Cpd-8 = 3/2/6: weight ratio) 0.70 Color mixing inhibitor (CPd-9) 0.05 Solvent (Solv-3) 0.42 Fifth layer (Red-sensitive layer) Monodisperse silver chlorobromide emulsion (EM11) spectrally sensitized with sensitizing dye (ExS-4,5) 0.07 Monodisperse spectrally sensitizing with sensitizing dye (ExS-4,5) Silver chlorobromide emulsion (EM12) 0.16 Gelatin 0.92 Cyan coupler (ExC-1) 1.46 Color image stabilizer (Cpd-7 / Cpd-8 / Cpd-10 = 3/4/2: weight ratio)
0.17 Dispersing polymer (Cpd-11) 0.14 Solvent (Solv-1) 0.20 Sixth layer (UV absorbing layer) Gelatin 0.54 UV absorber (Cpd-6 / Cpd-8 / Cpd-10 = 1/5/3: weight Ratio) 0.21 Solvent (Solv-4) 0.08 Seventh layer (protective layer) Gelatin 1.33 Acrylic modified copolymer of polyvinyl alcohol (Modification degree
17%) 0.17 Liquid paraffin 0.03 At this time, as an anti-irradiation dye,
(Cpd-12, Cpd-13) were used.

Further, for each layer, an emulsifying dispersant and an alkanol XC (Dupont), sodium alkylbenzenesulfonate, succinate, and Magefacx F-120 (manufactured by Nippon Ink Co., Ltd.) were used as coating aids. (Cpd-14, 15) 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 trioctyl phosphate Solv-3 trinonyl phosphate Solv-4 tricresyl phosphate After imagewise exposing the sample 101 obtained as described above,
Continuous processing was performed using an automatic processor until the cumulative replenishment amount of the color developing solution became three times the tank capacity. The treatment amount was 5 m ² per day. The processing steps are shown below.

The above replenishment amount indicates the replenishment amount per 1 m ² of the light-sensitive material. Further, as indicated by the arrow, the overflow of the washing water was conducted to the pre-bath by the countercurrent replenishment method, and the overflow of the washing water was led to the bleach-fixing solution. Continuous treatment: room temperature 20 ° C, humidity 75
%, Carbon dioxide concentration of 1200 ppm was performed indoors. The opening area of the automatic processor used in the experiment was 0.02 (cm ² / ml).
The evaporation amount per day was 60 ml. The operating time at this time was 10 hours.

The composition of each treatment liquid is as follows.

Bleach-fixing solution (same as tank solution and replenisher) Water 400ml Ammonium thiosulfate (70%) 200ml Sodium p-methylsulfinate 25g Sodium sulfite 20g Ethylenediaminetetraacetic acid iron (III) ammonium 100g Ethylenediaminetetraacetic acid disodium 5g Glacial acetic acid 7g Water 1000 ml pH (25 ℃) 5.80 Wash water (same as tank solution and replenisher) Tap water is H type strong basic cation exchange resin (Amberlite IR-120B manufactured by Rohm & Haas) and OH type anion exchange resin Water was passed through a mixed bed type column packed with (Amberlite IR-400) to give the following water quality.

Next, 40 ml of the washing water replenisher was added to the color developing solution every day at the end of the 1-day processing, and the continuous processing was carried out in the same manner as in the processing A (processing B). Further, the preservatives in the color developing solution were changed as shown in Table 1, and the continuous processing was carried out in the same manner as in the processing A (processing C). Further, the preservative was changed, and the other treatments were continuously performed as in the treatment B (treatments D to Q). The density change (ΔD _G min, ΔD _G max) of the magenta image before and after the continuous processing and the change of the yellow image density (ΔCB _1.0 ) at the point where the magenta image density was 1.0 were examined. The obtained results are shown in Table 1.

As is clear from Table 1, the processing method of the present invention produced favorable results with little change in photographic performance in continuous processing. Further, even in the case of a conventional color developing solution using hydroxylamine sulfate and potassium sulfite, which are preservatives for color developing solution, the effect of partially reducing the change in photographic property was recognized, but it cannot be said to be sufficient.

Example 2 Similar to No. 7 of Example 1, except that the preservative B was VII-
3, VIII-1, VIII-6, IX-3, IX-4, X-3, X
-8, XI-1, XI-2, XII-2, XII-10, XIII-1,
XIII-6, XIV-1, XIV-3, XV-1, XV-2, XVI-
When XVI-11 was used, excellent results were similarly obtained. Among them, the results of VII-3, XVI-1, and XVI-11 were excellent.

Example 3 On a subbed cellulose triacetate film support,
A sample 301, which is a multi-layer color light-sensitive material having the following composition, was prepared.

(Composition of photosensitive layer) The coating amount of silver halide and colloidal silver is silver.
The amount expressed in units of g / m ^2, also couplers, moles per 1 mol of silver halide in the same layer for the amount for the additives and gelatin expressed in units of g / m ^2, also the sensitizing dye Indicated by.

1st layer (anti-halation layer) Black colloidal silver …… 0.2 Gelatin 1.3 ExM-8 …… 0.06 UV-1 …… 0.1 UV-2 …… 0.2 Solv-1 …… 0.01 Solv-2 …… 0.01 Second layer ( Intermediate layer) Fine silver bromide (average particle size 0.07μ) …… 0.10 Gelatin …… 1.5 UV-1 …… 0.06 UV-2 …… 0.03 ExC-2 …… 0.02 ExF-1 …… 0.004 Solv-1 …… 0.1 Solv-2 ...... 0.09 Third layer (first red-sensitive emulsion layer) Silver iodobromide emulsion (AgI 2 mol%, internal high AgI type, spherical equivalent diameter 0.
3μ, coefficient of variation of spherical equivalent diameter 29%, normal crystal, twin crystal mixed particles, diameter / thickness ratio 2.5) Silver coating amount …… 0.4 Gelatin …… 0.6 ExS-1 …… 1.0 × 10 ^-4 ExS-2 …… 3.0 × 10 ^-4 ExS-3 …… 1 × 10 ^-5 ExS-3 …… 0.06 ExS-4 …… 0.06 ExS-7 …… 0.04 ExS-2 …… 0.03 Solv-1 …… 0.03 Solv-3 …… 0.012 4th layer (2nd red-sensitive emulsion layer) Silver iodobromide emulsion (AgI 5 mol%, internal high AgI type, spherical equivalent diameter 0.
7 microns, coefficient of variation of 25% equivalent spherical diameter, normal crystal, twin crystal mixed grains, diameter / thickness ratio 4) coating silver amount ...... 0.7 ExS-1 ...... 1 × 10 -4 ExS-2 ...... 3 × 10 - ⁴ ExS-3 …… 1 × 10 ^-5 ExC-3 …… 0.24 ExC-4 …… 0.24 ExC-7 …… 0.04 ExC-2 …… 0.04 Solv-1 …… 0.15 Solv-3 …… 0.02 5th layer (Second red-sensitive emulsion layer) Silver iodobromide emulsion (AgI 10 mol%, internal high AgI type, equivalent spherical diameter)
0.8μ, coefficient of variation of spherical equivalent diameter 16%, normal crystal, twin mixed particles, diameter / thickness ratio 1.3) Coating silver amount …… 1.0 Gelatin …… 1.0 ExS-1 …… 1 × 10 ^-4 ExS-2 ・ ・ ・… 3 × 10 ^-4 ExS-3 …… 1 × 10 ^-5 ExC-5 …… 0.05 ExC-6 …… 0.1 Solv-1 …… 0.01 Solv-3 …… 0.05 6th layer (intermediate layer) Gelatin …… 1.0 CpD-1 ...... 0.03 Solv-1 ...... 0.05 7th layer (1st green emulsion layer) Silver iodobromide emulsion (AgI 2 mol%, internal high AgI type, equivalent spherical diameter 0.
3.mu., coefficient of variation of 28% of the sphere-equivalent diameter, normal crystal, twin crystal mixed grains, diameter / thickness ratio 2.5) coating silver amount ...... 0.30 ExS-4 ...... 5 × 10 -4 ExS-6 ...... 0.3 × 10 - ⁴ ExS-5 …… 2 × 10 ^-4 Gelatin …… 1.0 ExM-9 …… 0.2 ExY-14 …… 0.03 ExM-8 …… 0.03 Solv-1 …… 0.5 Eighth layer (second green-sensitive emulsion layer) Silver iodobromide emulsion (AgI 4 mol%, internal high AgI type, spherical equivalent diameter 0.
6 [mu, variation coefficient 38% of equivalent spherical diameter, normal crystal, twin crystal mixed grains, diameter / thickness ratio 4) coating silver amount ...... 0.4 ExS-4 ...... 5 × 10 -4 ExS-5 ...... 2 × 10 - ⁴ ExS-6 …… 0.3 × 10 ^-4 ExM-9 …… 0.25 ExM-8 …… 0.03 ExM-10 …… 0.015 ExY-14 …… 0.01 Solv-1 …… 0.2 9th layer (3rd green emulsion) Layer) Silver iodobromide emulsion (AgI 6 mol%, internal high AgI type, spherical equivalent diameter 1.
0μ, coefficient of variation of sphere equivalent diameter 80%, normal crystal, twin mixed particles, diameter / thickness ratio 1.2) Coating silver amount …… 0.85 Gelatin …… 1.0 ExS-7 …… 3.5 × 10 ^-4 ExS-8 …… 1.4 × 10 ^-4 ExM-11 …… 0.01 ExM-12 …… 0.03 ExM-13 …… 0.20 ExM-8 …… 0.02 ExY-15 …… 0.02 Solv-1 …… 0.20 Solv-2 …… 0.05 10th layer (Yellow filter layer) Gelatin ...... 1.2 Yellow colloidal silver …… 0.08 Cpd-2 …… 0.1 Solv-1 …… 0.3 Eleventh layer (first blue sensitive emulsion layer) Silver iodobromide emulsion (AgI 4 mol%, internal) High AgI type, sphere equivalent diameter 0.
5μ, 15% variation coefficient of sphere equivalent diameter, octahedral grains) coated silver amount
…… 0.4 Gelatin …… 1.0 ExS-9 …… 2 × 10 ^-4 ExY-16 …… 0.9 ExY-14 …… 0.07 Solv-1 …… 0.2 12th layer (second blue emulsion layer) Silver iodobromide Emulsion (AgI 10 mol%, internal high AgI type, equivalent spherical diameter
1.3μ, coefficient of variation of equivalent spherical diameter 25%, normal crystal, twin mixed particles, diameter / thickness ratio 4.5) Coating silver amount …… 0.5 Gelatin …… 0.6 ExS-9 …… 1 × 10 ^-4 ExS-8… … 1.4 × 10 ^-4 ExY-16 …… 0.25 Solv-1 …… 0.07 13th layer (first protective layer) Gelatin …… 0.8 UV-1 …… 0.1 UV-2 …… 0.2 Solv-1 …… 0.01 Solv -…… 0.01 14th layer (2nd protective layer) Fine silver bromide (average particle size 0.07μ) …… 0.5 Gelatin …… 0.45 Polymethylmethacrylate particles (diameter 1.5μ) …… 0.2 H-1 …… 0.4 Cpd-3 ... 0.5 Cpd-4 ... 0.5 In addition to the above components, a surfactant was added to each layer as a coating aid. The sample prepared as described above is sample 101
And

Next, the chemical structural formulas or chemical names of the compounds used in the present invention are shown below.

Solv-1 Tricresyl phosphate Solv-2 Dibutyl phthalate Solv-3 Bis (2-ethylhexyl) phthalate The sample manufactured as described above was designated as 101.

The above sample was cut into a width of 35 mm and a length of 110 cm, and after being subjected to photographing, the same washing water as in Example-1 was used in the following processing steps,
For 10 days a day for each, 4 weeks (22 working days)
Processed.

The processing steps are as shown in Table 3.

* All overflows from water washing (1) were introduced into the bleach-fix bath. As the processor, a negative processor FP-350 for Cyan Pion 23S manufactured by Fuji Photo Film Co., Ltd. was used after being modified.
The amount of the bleach-fix solution brought into the washing with this processor was 2 ml per 1 m of width of 35 mm.

Next, the composition of the treatment liquid will be described.

(Stabilizer) Tank solution, replenisher common (unit: g) Formalin (37%) 2.0 ml Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization 10) 0.3 Ethylenediaminetetraacetic acid disodium salt 0.05 Add water 1.0 L pH 5.0-8.0 A part of the washing water replenisher was added to the color developer. The amount of water added and the addition method of the washing replenisher are shown in Table 2. The processor performs continuous processing under the same environmental conditions as in the first embodiment. The opening area of the color developing tank was 0.015, and the evaporation amount of the color developing solution was 100 ml / day. The operating time was 10 hours a day. Minimum density change of cyan image before and after continuous processing (ΔD _R
min) and the gradation change (Δγ _R ) of the cyan image.
The results obtained are shown in Table 2.

As is clear from Table 2, the processing method of the present invention provided favorable results with little change in photographic property in continuous processing. Moreover, the amount of water added per day is 40-80 ml (0.
4 to 0.8 times) (No.4,5,6,9,10,1)
1,14,15,16), irrespective of the frequency of addition, particularly favorable results with stable photographic properties were obtained.

Example 5 In the same manner as in Example 4, except that the exemplified compound I-1 was replaced with III-7, I
Excellent performance was obtained when the same treatment was carried out under the conditions of Example 4, No. 5, except for changing to II-12, III-22 and III-25.

Example 6 Paper support laminated on both sides with polyethylene (thickness 100
Micron) was coated on the front side with the following first to fourteenth layers, and on the back side with a multi-layer coating of the fifteenth to sixteenth layers to prepare a color photographic light-sensitive material. The polyethylene on the coating side of the first layer contains titanium chloride as a white pigment and a trace amount of ultramarine as a bluing dye (the chromaticity of the surface of the support is L ^* , a ^* , b ^*
The values were 8.0, -0.20 and -0.75. ) (Photosensitive layer composition) The components and the coating amount (g / m ² unit) are shown below. For silver halide, the coating amount in terms of silver is shown. The emulsion used for each layer was produced according to the production method of Emulsion EM1. However, as the 14th layer emulsion, a Lippmann emulsion which was not surface chemically sensitized was used.

First layer (anti-halation layer) Black colloidal silver ・ ・ ・ 0.10 Gelatin ・ ・ ・ 0.70 Second layer (intermediate layer) Gelatin ・ ・ ・ 0.70 Third layer (low sensitivity red sensitive layer) Red sensitizing dye (ExS-1) , 2,3) spectrally sensitized silver bromide (average grain size 0.25μ, size distribution [variation coefficient] 8
%, Octahedron) ・ ・ ・ 0.04 Silver chlorobromide spectrally sensitized with red sensitizing dye (ExS-1,2,3) (5 mol% silver chloride, average particle size 0.40μ, size distribution)
10%, octahedron) ・ ・ ・ 0.08 Gelatin ・ ・ ・ 1.00 Cyan coupler (ExC-1, 2 equivalents) ・ ・ ・ 0.30 Anti-fading agent (Cpd-1, 2, 3, 4 equivalents) ・ ・ ・ 0.18 Anti-stain agent (Cpd-5) ・ ・ ・ 0.003 Coupler dispersion medium (Cpd-6) ・ ・ ・ 0.03 Coupler solvent (Solv-1, 2, 3 equivalents) ・ ・ ・ 0.12 4th layer (high sensitivity red sensitive layer) ) Silver bromide spectrally sensitized with red sensitizing dye (ExS-1,2,3) (average grain size 0.60μ, size distribution 15%, octahedron)
・ ・ 0.14 Gelatin ・ ・ ・ 1.00 Cyan coupler (ExC-1, 2 equivalents) ・ ・ ・ 0.30 Anti-fading agent (Cpd-1, 2, 3, 4 equivalents) ・ ・ ・ 0.18 Coupler dispersion medium (Cpd-6) ) ・ ・ ・ 0.03 Coupler solvent (Solv-1, 2, 3, equivalent) ・ ・ ・ 0.12 Fifth layer (intermediate layer) Gelatin ・ ・ ・ 1.00 Color mixing inhibitor (Cpd-7) ・ ・ ・ 0.08 Color mixing inhibitor Solvent (Solv-4, 5 equivalents) ... 0.16 Polymer latex (Cpd-8) ... 0.10 6th layer (low sensitivity green sensitive layer) Spectral sensitized with green sensitizing dye (ExS-4) Silver bromide (average grain size 0.25μ, size distribution 8%, octahedron) ...
0.04 Silver chlorobromide spectrally sensitized with a green sensitizing dye (ExS-4) (5 mol% silver chloride, average grain size 0.40μ, size distribution
10%, octahedron) ・ ・ ・ 0.06 Gelatin ・ ・ ・ 0.80 Magenta coupler (ExM-1, 2 equivalents) ・ ・ ・ 0.11 Anti-fading agent (Cpd-9) ・ ・ ・ 0.10 Anti-stain agent (Cpd-10, (11, 12, 13 in 10: 7: 7: 1 ratio)
・ ・ ・ 0.025 Coupler dispersion medium (Cpd-6) ・ ・ ・ 0.05 Coupler solvent (Solv-4, 6 equivalents) ・ ・ ・ 0.15 7th layer (high sensitivity green sensitive layer) Green sensitizing dye (ExS-4) Silver bromide spectrally sensitized by (average grain size 0.65μ, size distribution 16%, octahedron) ...
0.10 Gelatin: 0.80 Magenta coupler (ExM-1, 2 equivalents): 0.11 Anti-fading agent (Cpd-9): 0.10 Anti-staining agent (Cpd-10, 11, 12, 13 at 10: 7) : 7: 1 ratio)
・ ・ ・ 0.025 Coupler dispersion medium (Cpd-6) ・ ・ ・ 0.05 Coupler solvent (Solv-4, 6 equivalents) ・ ・ ・ 0.15 8th layer (intermediate layer) Same as 5th layer 9th layer (yellow filter layer) ) Yellow colloidal silver ・ ・ ・ 0.12 Gelatin ・ ・ ・ 0.07 Color mixing inhibitor (Cpd-7) ・ ・ ・ 0.03 Color mixing inhibitor solvent (Solv-4, 5 equivalents) ・ ・ ・ 0.10 Polymer latex (Cpd-8) ・..0.07 10th layer (intermediate layer) Same as 5th layer 11th layer (low sensitivity blue sensitive layer) Silver bromide spectrally sensitized with blue sensitizing dye (ExS-5, 6) (average grain size 0.40 μ, size distribution 8%, octahedron) ・
..0.07 Silver chlorobromide spectrally sensitized with blue sensitizing dye (ExS-5, 6) (silver chloride 8 mol%, average grain size 0.60 μ, size distribution 11%, octahedron) ・ ・ ・ 0.14 Gelatin・ ・ ・ 0.80 Yellow coupler (ExY-1) ・ ・ ・ 0.35 Anti-fading agent (Cpd-14) ・ ・ ・ 0.10 Anti-staining agent (Cpd-5,15 in 1: 5 ratio) ・ ・ ・ 0.007 Coupler dispersion medium (Cpd-6) ・ ・ ・ 0.05 Coupler solvent (Solv-2) ・ ・ ・ 0.10 12th layer (high sensitivity blue sensitive layer) Silver bromide spectrally sensitized with blue sensitizing dye (ExS-5, 6) (Average particle size 0.85μ, size distribution 18%, octahedron) ・
・ ・ 0.15 Gelatin ・ ・ ・ 0.60 Yellow coupler (ExY-1) ・ ・ ・ 0.30 Anti-fading agent (Cpd-14) ・ ・ ・ 0.10 Anti-staining agent (Cpd-5,15 in 1: 5 ratio) ・ ・ ・0.007 Coupler dispersion medium (Cpd-6) ・ ・ ・ 0.05 Coupler solvent (Solv-2) ・ ・ ・ 0.10 Layer 13 (UV absorbing layer) Gelatin ・ ・ ・ 1.00 UV absorber (Cpd-2, 4, 16 equivalents) ) ・ ・ ・ 0.50 Color mixing inhibitor (Cpd-7, 17 equivalents) ・ ・ ・ 0.03 Dispersion medium (Cpd-6) ・ ・ ・ 0.02 UV absorber solvent (Solv-2, 7 equivalents) ・ ・ ・ 0.08 Anti-radiation dye (Cpd-18, 19, 20, 21 10: 1
0.04 14th layer (protective layer) Fine silver chlorobromide (97 mol% silver chloride, average size 0.2μ)
・ ・ ・ 0.03 Acrylic modified copolymer of polyvinyl alcohol ・ ・ ・ 0.
01 Polymethylmethacrylate particles (average particle size 2.4
μ) and silicon oxide (average particle size 5μ) are equivalent ...
05 Gelatin ・ ・ ・ 1.80 Gelatin hardening agent (H-1, H-2 equivalent) ・ ・ ・ 0.18 Fifteenth layer (back layer) Gelatin ・ ・ ・ 2.50 Sixteenth layer (back surface protection layer) Polymethylmethacrylate particles (average) Particle size 2.4
μ) and silicon oxide (average particle size 5μ) are equivalent ...
05 Gelatin ・ ・ ・ 2.00 Gelatin hardening agent (H-1, H-2 equivalent) ・ ・ ・ 0.14 How to make emulsion EM-1 Potassium bromide and silver nitrate aqueous solution is stirred vigorously in gelatin aqueous solution for 15 minutes at 75 ℃. Were added simultaneously to obtain octahedral silver bromide grains having an average grain size of 0.40μ. 0.3 g of 3,4-dimethyl-1,3-thiazoline-mole per mol of silver was added to this emulsion.
2-Thion, 6 mg of sodium thiosulfate and 7 mg of chloroauric acid (4 mercury) were sequentially added, and the mixture was heated at 75 ° C. for 80 minutes for chemical sensitization. The grains thus obtained were used as cores and further grown in the same precipitation environment as in the first time, to finally obtain an octahedral monodisperse core / shell silver bromide emulsion having an average grain size of 0.7μ. The coefficient of variation of particle size was about 10%.
To this emulsion, 1.5 mg of sodium thiosulfate and 1.5 mg of chloroauric acid (tetrahydrate) were added per mol of silver, and the mixture was heated at 60 ° C. for 60 minutes for chemical sensitization to obtain an internal latent image type silver halide emulsion. Obtained.

In each photosensitive layer, nucleating agents ExZK-1 and ExZK-2 were added in an amount of 10 ^-3 % by weight based on the silver halide, and Cpd-22 as a nucleating accelerator.
^Was used at 10 ^-2 % by weight. Further, in each layer, alkanol XC (Dupon Co.) and sodium alkylbenzene ring sulfonate were used as emulsification / dispersion aids, and succinate ester and Magefac F-120 (manufactured by Dainippon Ink and Chemicals) were used as coating aids.
(Cpd-23, 25, 25) was used as a stabilizer in the layer containing silver halide and colloidal silver. The compounds used in the examples are shown below.

Solv-1 Di (2-ethylhexyl) sebacate Solv-2 Trinonyl phosphate Solv-3 Di (3-methylhexyl) phthalate Solv-4 Tricredys phosphate Solv-5 Dibutyl phthalate Solv-6 Trioctyl phosphate Solv-7 Di (2 -Ethylhexyl) phthalate H-1 1,2-bis (vinylsulfonylacetamide)
Ethane H-2 4,6-dichloro-2-hydroxy-1,3,5-triazine Na salt ExZK-1 7- [3- (5-mercaptotetrazole-
1-yl) benzamido] -10-propal-1,2,3,4-tetrahydromacridinium perchlorate ExZK-2 1-formyl-2- {4- [3- {3- [3
-(5-Mercaptotetrazol-1-yl) phenyl] ureido} benzenesulfonamide] phenyl} hydrazine After imagewise exposing the silver halide color photographic light-sensitive material 401 prepared as described above, an automatic processor was used. By the method described below, continuous processing was carried out at 0.6 m ² per day until the cumulative replenishment amount of the color developing solution became 1.5 times the tank capacity.

The replenishing method of washing water is such that the washing bath (3) is replenished, the overflow solution of the washing bath (3) is introduced into the washing bath (2), and the overflow solution of the washing bath (2) is introduced into the washing bath (1). The so-called countercurrent replenishment method was adopted. At this time, the carry-in amount of the bleach-fixing solution from the bleach-fixing bath to the washing bath (1) by the light-sensitive material was 35 ml / m ² , and the ratio of the replenishing amount of washing water to the carry-in amount of the bleach-fixing solution was 9.1 times.

The composition of each treatment liquid was as follows.

Rinse water Same as in Example 1 Next, the rinsing water was changed to the rinsing alternative stabilizing solution (A) having the following composition, and the same continuous treatment was performed.

Next, the ammonia water (26%) of the washing substitute stabilizer A was replaced with sodium hydroxide, and the washing substitute stabilizer B was prepared in the same manner as the washing substitute stabilizer A, and the continuous treatment was performed.

The change in photographic property before and after the continuous processing was examined in the same manner as in Example 1. The opening area of the automatic processor used in this experiment was 0.005 (cm ² / ml), and the amount of evaporation per day was 60 ml under the same environment as in Example 1. Subsequently, continuous processing was carried out while adding a washing solution replenishing solution and a washing substitute stabilizing solution replenishing solution to examine changes in photographic properties. The results obtained are shown in Table 3.

As is clear from Table 3, the processing method of the present invention provided favorable results with little change in photographic performance in continuous processing. Stabilizer A containing ammonia water (26%)
When the treatment was carried out using the above-mentioned solution, the change in the minimum concentration was large and slightly inferior to the case where the treatment was carried out using the stabilizing solution B containing no ammonia water. It is considered that this is because fogging was caused by ammonia in the stabilizing solution.

Example 7 Exemplified Compound II as in Example 6 but in color developer
Instead of I-7, I-1, I-2, II-2, III-12, III
-22, IV-8, and V-1 were used to add water. Similarly, the change in photographic property during continuous processing was small, and good results were obtained.

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Claims (2)

[Claims] 1. A method for continuously processing an imagewise exposed silver halide color photographic light-sensitive material by using an automatic processor, wherein a color developing bath of the automatic processor is supplemented with water or a washing substitute stabilizer. A silver halide color characterized in that the color developing solution contains an organic preservative and the replenishing amount of the color developing solution is 20 to 600 ml per 1 m ^{2 of the} light-sensitive material. Processing method of photographic light-sensitive material. 2. The amount of replenishment of the washing bath or the washing substitute stabilizer in the washing bath or the stabilizing bath alternative to washing is 1 to 50 times the carried-in amount of the pre-bath component by the light-sensitive material. The processing method according to item (1).