JPH07120900A - Method for processing silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To remarkably improve the stability, desilverizing property and color developing property (prevention of leuco compd. formation) of a bleach fixer and to drastically reduce the replenishment of the bleach fixer and the amt. of waste soln. CONSTITUTION:In the procesing method in which a silver halide color photographic sensitive material is developed and then processed with a bleach fixer, the surface of a bleach fixer in its feed tank is covered with a fluid layer floating on the surface, and the opening ratio of a bleaching and fixing tank (ratio of the area (cm<2>) where the liq. is in contact with air to the tank volume (cm<3>) of the processing soln.) is controlled to be 0.002-0.02cm<-1>.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for processing a silver halide color photographic light-sensitive material, and more particularly to a processing method in which the stability, desilvering property and color recoloring property of a bleach-fixing solution are remarkably improved.

[0002]

BACKGROUND OF THE INVENTION The processing of silver halide color photographic light-sensitive materials basically comprises two steps of color development and desilvering. Desilvering is a bleaching and fixing step, or one-bath bleaching used in combination with these or alone. It consists of a fixing process. If necessary, additional processing steps such as water washing, stopping processing, stabilizing processing, pretreatment for promoting development and the like are added. In recent years, reducing the amount of replenishment of bleach-fixing solution and reducing the amount of waste solution have made it possible to reduce the environmental pollution as well as speed up the bleach-fixing process.
It is strongly desired for resource saving and cost reduction.
However, the reality is that low replenishment and low liquid waste have not been achieved. The main reason is that there was no technology to improve the stability of the bleach-fix solution. Specifically, the low replenishment lengthens the retention time of the processing solution in the bleach-fixing bath and causes stains due to the reduction of sulfite which is a preservative. The problem is that precipitation of sulfur and silver sulfide occurs in the washing and / or stabilizing solution. Another reason is
The problem is that the mixing ratio of the color developing solution becomes high, the desilvering property deteriorates, and the coloring property decreases due to leuco conversion of the cyan dye.

For the purpose of improving the stability of the bleach-fixing solution, a patent for a carbonyl bisulfite adduct has been filed (Japanese Patent Laid-Open Nos. 48-42733 and 50-5).
No. 1326, No. 56-107244, JP-A-1-26
7540, JP-A-3-233451). However, with the above technique, the stability of the bleach-fix solution is insufficiently improved,
Remarkably low replenishment was difficult. In particular, if the concentration of the preservative such as a sulfite salt or a carbonyl bisulfite adduct is increased, a new problem arises in that the desilvering property is lowered and the cyan dye is converted into leuco. In recent years, minilabs, which have been introduced to the market in recent years, have no technology that can significantly reduce the replenishment amount even when the processing amount is small and the processing solution stays for a long time. It was necessary to develop a new technology that is compatible with prevention of degeneration.

[0004]

Therefore, the first aspect of the present invention
It is an object of the invention to provide a processing method with improved stability of the bleach-fix solution. A second object is to provide a processing method having a good desilvering property and preventing the leuco conversion of the cyan dye. A third object is to provide a processing method in which the replenishing amount of the bleach-fixing solution is remarkably reduced.

[0005]

DISCLOSURE OF THE INVENTION As a result of examining the above problems, the present inventors have found that the object can be achieved by the following processing method.

(1) In the method of processing a silver halide color photographic light-sensitive material with a bleach-fixing solution after color development, the surface of the bleach-fixing replenisher in a bleach-fixing replenisher tank is covered with a fluid layer of a floating fluid. , Opening ratio of bleach-fix processing tank (Area in which the liquid contacts the air (cm ² ) with respect to the total processing liquid (cm ³ ))
Ratio) is 0.002 to 0.02 cm ⁻¹ , the method for processing a silver halide color photographic light-sensitive material. (2) The processing method according to (1), wherein the floating fluid is liquid paraffin or liquid saturated hydrocarbon. (3) The bleach-fixing replenisher contains 0.15 organic iron complex salt.
The treatment method according to (1) or (2), which contains 0.35 mol / liter. (4) The circulating amount of the bleach-fixing solution in the bleach-fixing processing tank is 1
The treatment method according to (1), (2) and (3), which is 30 to 150% of the total amount of the treatment liquid per minute.

In order to improve the stability of the bleach-fixing solution, the present invention has found that stabilizing the bleach-fixing replenisher is more effective than the bleach-fixing solution (processing tank solution). It is based on that. First, as a means for preventing the preservative deterioration of the replenisher, the present inventors can completely prevent air oxidation of the preservative by coating the liquid surface of the replenisher with a fluid layer formed by a floating fluid, which is extremely stable. I found that I can improve. However, if this replenisher is used as it is, the desilvering property is deteriorated and the leuco cyanation occurs due to the ferrous organic acid ferric salt produced by the reaction between the preservative and the ferric organic acid salt. There was a problem. In contrast,
By making the bleach-fixing treatment tank have a specific opening ratio (ratio of the contact area with air to the total amount of treatment liquid in the treatment tank), conversely, air oxidation is used to return ferrous organic acid salts to ferric iron salts. It has been found that it is possible to solve the problems of desilvering and leuco formation of cyan dye. In the present invention, the replenisher tank refers to a tank that stores the replenisher (also referred to as a replenisher tank), and the photosensitive material is not processed in the replenisher tank. The processing tank refers to a tank (also called a processing tank) in which the photosensitive material is dipped and processed. In this way, the replenisher tank and the processing tank are clearly distinguished. In this way, by covering the replenisher with a fluid layer and a processing tank having a specific opening ratio, and controlling the air oxidation, it is possible to achieve remarkable stabilization, good desilvering properties, and prevention of leuco formation.

Japanese Patent Laid-Open No. 1-310351 discloses a technique of preventing evaporation of the processing liquid, lowering of the liquid level, and air oxidation by coating the surface of the processing liquid of the developing solution with a fluid layer of a floating fluid. Is disclosed. The above-mentioned application is for adding a fluid to the processing tank and is not practically usable due to uneven processing, and when used in a bleach-fixing processing tank, the effect of improving the stability of the liquid as described above is obtained. Almost never
On the contrary, the desilvering failure due to the formation of the ferric salt of the organic acid and the leuco conversion of the cyan dye occurred, which was not practical. The above application basically relates to a developer,
There is no description about stabilization and desilvering property of the bleach-fixing solution of the present invention, and the present invention is not considered at all.

The fluid floating in the bleach-fix replenisher will be described. The specific gravity of the bleach-fix replenisher is usually 1.050.
The specific gravity of the bleach-fixing replenisher is lower than the specific gravity of the bleach-fixing replenisher in order to float. The specific gravity of the floating fluid is preferably 1.030 or less, more preferably 1.000 or less, and particularly preferably 0.950 or less. It is preferably 0.6 or more, more preferably 0.
7 or more. The floating fluid needs to form a fluid layer, and must be compatible and immiscible with the replenisher. The water content of the fluid is preferably 10% by weight or less, more preferably 1% by weight or less, and particularly preferably 0.2% by weight or less.
It is preferable that the floating fluid does not evaporate. The boiling point of the fluid is preferably 100 ° C or higher, more preferably 150 ° C or higher, and particularly preferably 200 ° C or higher. The upper limit is not particularly limited, and the higher the upper limit, the more preferable because it is less likely to evaporate.

The floating fluid does not adversely affect the photographic characteristics and processability of the light-sensitive material by reacting with the bleach-fix replenisher and has a relatively low dielectric constant (relative permittivity 2 to 20). It is preferable that it is about). Specific examples of the floating fluid include liquid saturated hydrocarbon such as paraffin and cycloparaffin, phosphoric acid ester, phthalic acid ester,
Examples thereof include various synthetic oils such as benzoic acid ester, substituted benzoic acid ester, lactic acid ester, fatty acid ester, benzyl alcohol ester, carbonic acid ester, ether type, active methylene type and alcohol type compounds. Liquid paraffin and liquid saturated hydrocarbon are preferable.

Specific compounds are listed below, but the invention is not limited thereto. 1) Liquid paraffin Specific gravity 0.881 Boiling point 300 ° C or higher 2) Nonane 0.718 150 ° C 3) Decane 0.730 174 ° C 4) Undecane 0.740 196 ° C 5) Dodecane 0.749 216 ° C 6) Tridecane 0.757 234 ° C 7) Tetradecane 0.764 251 ° C 8) Pentadecane 0.769 268 ° C. Here, for example, the following liquid paraffin can be easily obtained. Product name Specific gravity (37.8 ℃) CARNATION (manufactured by Ito Corporation) 0.842 SUS 72.31 CST 13.67 KAYDOL (〃) 0.880 354.8 76.55

Among the above compounds, the compounds (1) to (8) are preferable, and in particular (1) liquid paraffin has a high boiling point, a low water content, no compatibility with the replenisher, and no replenishment. It is highly preferable because it has no reaction with the liquid components and the solubility of the oil-soluble component in the replenisher, has little oxygen absorption and carbon dioxide absorption. The thickness of the fluid layer is preferably about 0.1 to 20 mm. Further, it is also preferable to use in combination with the floating body disclosed in JP-A-61-258245.

The bleach-fixing solution and the bleach-fixing replenisher will be described below. In the present invention, the opening ratio of the bleach-fixing treatment tank (ratio of the area (cm ² ) where the liquid contacts air with respect to the total amount of processing liquid (cm ³ ) in the bleach-fixing treatment tank) is 0.002 to 0.0.
It must be 2 cm ^-1 . Preferably 0.004
To 0.018 cm ^-1 , especially 0.005 to 0.015
It is preferably cm ^-1 . In the present invention, the bleach-fixing replenisher contains 0.10 to 1.0 per liter of the replenisher.
The organic acid iron complex salt may be contained in an amount of 0.15 to 0.4 mol / liter, particularly from the viewpoint of stability of the replenisher and desilvering property and prevention of leuco cyanation of the cyan dye. , 0.20 to 0.30 mol / liter is preferable. In the present invention, the bleach-fixing solution can contain 0.02 to 0.50 mol of organic acid iron complex salt per liter of the processing solution, but the stability of the processing solution, desilvering property and cyan dye From the point of leuco prevention, 0.05-
0.30 mol / liter, particularly 0.08 to 0.20 mol / liter is preferable. Examples of the organic acid compound forming the organic acid iron complex salt used as the bleach-fixing solution bleaching agent include ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid,
Ethylenediamine-N- (β-oxyethyl) -N,
N ', N'-triacetic acid, 1,2-diaminopropanetetraacetic acid, 1,3-diaminopropanetetraacetic acid, nitrilotriacetic acid, nitrilo-N-2-carboxy-N, N-diacetic acid,
N- (2-acetamido) iminodiacetic acid, cyclohexanediaminetetraacetic acid, iminodiacetic acid, dihydroxyethylglycine, ethyletherdiaminetetraacetic acid, glycoletherdiaminetetraacetic acid, ethylenediaminetetrapropionic acid, phenylenediaminetetraacetic acid, 1,3- Diaminopropanol-N, N, N ', N'-tetramethylenephosphonic acid, ethylenediamine-N, N, N', N'-tetramethylenephosphonic acid, 1,3-propylenediamine-N,
Examples thereof include N, N ', N'-tetramethylenephosphonic acid, their sodium salts and ammonium salts. Among the above, 1,3-diaminopropane tetraacetic acid, nitrilo-
N-2-carboxy-N, N-diacetic acid, N- (2-acetamido) iminodiacetic acid and ethylenediaminetetraacetic acid are particularly preferred. Further, a compound represented by the following general formula (E) is also particularly preferable. General formula (E)

[0014]

[Chemical 1]

(In the formula, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ each represent a hydrogen atom, an aliphatic group, an aromatic group or a hydroxy group. W represents a divalent group containing a carbon atom. M ₁ , M ₂ , M ₃ and M ₄ each represent a hydrogen atom or a cation.) Specific examples of the compound represented by formula (E) are shown below.

[0016]

[Chemical 2]

[0017]

[Chemical 3]

[0018]

[Chemical 4]

The compound represented by the general formula (I) may be any optical isomer. [S. S] body, [S.
R] body, [R. S] body, [R. R] -form, or a mixture of these isomers. Above all,
In the present invention, from the viewpoint of stability, desilvering property and biodegradability of the bleach-fixing solution, [S. Compounds synthesized from L-amino acid as a raw material such as S] -form are particularly preferable.

In the present invention, as the bleaching agent, the above-mentioned iron complex salts of organic acids may be used alone or in combination of two or more kinds.

In the present invention, the circulation amount of the bleach-fixing solution in the bleach-fixing treatment tank is 30 to 150% of the total amount of the bleach-fixing solution (total amount including the processing tank and the circulation system) per minute. It is preferable in terms of stability of the bleach-fixing solution, desilvering property, and prevention of leuco formation of the cyan dye. More preferably 40-
It is 120%, and particularly preferably 50 to 100%.

Next, the desilvering process applicable to the present invention will be described. In the present invention, the desilvering step includes a bleach-fixing step, and includes a bleach-fixing step, a bleach-bleach-fixing step, a bleach-fixing step-fixing step, a bleaching step-bleach-fixing step-fixing step and the like. In the present invention, the bleach-fixing step alone is preferable in terms of simplifying and speeding up the desilvering step.

Next, another composition of the bleach-fixing solution of the present invention will be described. The bleach-fixing solution preferably contains a halide such as chloride, bromide or iodide as a rehalogenating agent for promoting silver oxidation. Further, an organic ligand that forms a sparingly soluble silver salt may be added instead of the halide. The silver halide is added as an alkali metal salt or ammonium salt, or a salt of guanidine, amine or the like. Specifically, potassium bromide, sodium bromide,
There are ammonium bromide, potassium chloride, guanidine hydrochloride, etc., preferably potassium bromide or sodium bromide. The amount of the rehalogenating agent in the bleaching solution is suitably 2 mol / liter or less, preferably 0.001 to 2.0 mol / liter, and more preferably 0.1 to 1.0 mol / liter.

In addition to the bleach-fixing solution according to the present invention, a bleaching accelerator, a corrosion inhibitor for preventing corrosion of the processing bath, and a pH of the solution.
A buffering agent, a fluorescent whitening agent, a defoaming agent, etc. for maintaining the above are added as necessary. Examples of bleaching accelerators include US Pat. No. 3,893,858, German Patent 1,290,
812, U.S. Pat. No. 1,138,842, JP-A-5
3-95630, Research Disclosure No. 1
No. 7129 (1978), a compound having a mercapto group or a disulfide group, JP-A-50-14012.
Thiazolidine derivatives described in Japanese Patent Publication No. 9, US Pat.
706,561 thiourea derivatives, German Patent No. 2,748,430 polyethylene oxides, JP-B-45-8836 polyamine compounds, JP-A-49-40493 imidazole compounds, etc. Can be used. Among them, the mercapto compounds described in US Pat. No. 1,138,842 are preferable. As the corrosion inhibitor, nitrate is preferably used, and ammonium nitrate, sodium nitrate, potassium nitrate or the like is used. The amount added is 0.01-
It is 2.0 mol / liter, preferably 0.05 to 0.5 mol / liter. In the bleach-fixing solution according to the present invention, the total ammonium ion concentration is preferably 0.3 gram ion / liter or less. This embodiment is preferable from the viewpoint of image storability and environmental protection, and in the present invention, it is more preferably 0.1 mol / liter or less. Any pH buffer may be used as long as it is not easily oxidized by a bleaching agent and has a buffering effect in a pH range of 3.0 to 8.0. For example, acetic acid, glycolic acid, lactic acid, propionic acid, butyric acid,
Malic acid, chloroacetic acid, levulinic acid, ureidopropionic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, β-
Organic acids such as hydroxypropionic acid, tartaric acid, citric acid, oxalacetic acid, diglycolic acid, benzoic acid and phthalic acid, pyridine, dimethylpyrazole, 2-methyl-o
-Oxazolines, organic bases such as aminoacetonitrile, and phosphoric acid, or imidazoles such as imidazole, 1-methyl-imidazole, 2-methyl-imidazole, 1-ethylimidazole, triethanolamine, N-allylmorpholine, N-benzoyl piperazine etc. are mentioned. The total amount of these buffers used is suitably 3.0 mol or less, preferably 0.1 to 1.0 mol, per liter of the bleach-fixing solution.

A known fixing agent is used in the bleach-fixing solution. These are thiosulfates, thiocyanates, thioethers, amines, mercaptos, thiones, thioureas, iodides, mesoions and the like, and examples thereof include ammonium thiosulfate, sodium thiosulfate, potassium thiosulfate and thiosulfate. Guanidine sulfate, potassium thiocyanate,
Dihydroxyethyl-thioether, 3,6-diathi-
Examples include 1,8-octanediol and imidazole. Of these, thiosulfates, particularly ammonium thiosulfate, are preferred for rapid fixing. Further, by using two or more fixing agents in combination, more rapid fixing can be performed. For example, in addition to ammonium thiosulfate, it is also preferable to use the above-mentioned ammonium thiocyanate, imidazole, thiourea, thioether and the like together. In this case, the second fixing agent is 0.01 to 10 with respect to ammonium thiosulfate.
It is preferably added in the range of 0 mol%. The amount of the fixing agent is 0.1 to 3.0 mol, preferably 0.5 to 2.0 mol, per liter of the bleach-fixing solution.

A preservative may be added to the bleach-fixing solution to enhance the stability of the solution over time. In the case of a bleach-fixing solution or a fixing solution containing thiosulfate, sulfite as a preservative, and / or hydroxylamine, hydrazine,
Aldehyde bisulfite adduct (for example, acetaldehyde bisulfite adduct, particularly preferably JP-A 1-2)
The bisulfite adduct of an aromatic aldehyde described in No. 98935) is effective. It is also preferable to use the sulfinic acid compounds described in JP-A-62-143048.

The sulfinic acid or its salt will be described in detail below. General formula (S)

[0028]

[Chemical 5]

(Wherein R is an alkyl group, an alkenyl group,
It represents an aralkyl group, a cycloalkyl group, an aryl group or a heterocyclic group, and M represents a cation. n is 1 or 2
Is. ) Hereinafter, the general formula (S) will be described in detail. R is a substituted or unsubstituted alkyl group (methyl group, ethyl group, n-propyl group, hydroxyethyl group,
Sulfoethyl group, carboxyethyl group, methoxyethyl group, etc.), substituted or unsubstituted alkenyl group (allyl group, butenyl group, etc.), substituted or unsubstituted aralkyl group (benzyl group, phenethyl group, 4-carboxyphenylmethyl) Group, 3-sulfophenylmethyl group, etc.), substituted or unsubstituted cycloalkyl group (cyclohexyl group, etc.), substituted or unsubstituted aryl group (phenyl group, 4-methylphenyl group, naphthyl group, 3-carboxy) Phenyl group, 4-methoxyphenyl group, 3-sulfophenyl group, 4-carboxymethoxyphenyl group, 3-carboxymethoxyphenyl group, 4-carboxyethoxyphenyl group, 4-sulfoethoxyphenyl group, 4-carboxymethylphenyl group, 4- (N-carboxymethyl-N-methyl) phenyl Nyl group, etc.) or a substituted or unsubstituted heterocyclic group (pyridyl group, furyl group, thienyl group, pyrazolyl group, indolyl group, etc.), M is a cation (hydrogen atom, alkali metal, alkaline earth metal) metal,
And nitrogen-containing organic bases or ammonium groups).

Alkali metals include Na, K, Li, etc.
Examples of the alkaline earth metal include Ca and Ba, examples of the nitrogen-containing organic base include usual amines capable of forming a salt with sulfinic acid, and examples of the ammonium group include an unsubstituted ammonium group and a tetramethylammonium group. When R represented by the general formula (S) has a substituent,
Examples thereof include nitro group, halogen atom (base atom, bromine atom, etc.), cyano group, alkyl group (methyl group, ethyl group, propyl group, carboxymethyl group, carboxyethyl group, carboxypropyl group, sulfoethyl group, sulfo group). Propyl group, dimethylaminoethyl group, etc.), aryl group (phenyl group, naphthyl group, carboxyphenyl group, sulfophenyl group, etc.), alkenyl group (allyl group, butenyl group, etc.), aralkyl group (benzyl group, phenethyl group, etc.) Group, etc.), sulfonyl group (methanesulfonyl group, p-toluenesulfonyl group, etc.), acyl group (acetyl group, benzoyl group, etc.), carbamoyl group (unsubstituted carbamoyl group, dimethylcarbamoyl group, etc.), sulfamoyl group (Unsubstituted sulfamoyl group, methylsulfamoyl group, dimethyls Famoiru group, etc.), a carbonamido group (acetamido group, benzamido group, etc.),
Sulfonamide group (methanesulfonamide group, benzenesulfonamide group, etc.), acyloxy group (acetyloxy group, benzoyloxy group, etc.), sulfonyloxy group (methanesulfonyloxy group, etc.), ureido group (unsubstituted ureido group) , Etc.), thioureido group (unsubstituted thioureido group, methylthioureido group, etc.), carboxylic acid or salt thereof, sulfonic acid or salt thereof, hydroxy group,
Alkoxy group (methoxy group, ethoxy group, carboxyethoxy group, carboxymethoxy group, sulfoethoxy group,
Sulfopropyloxy group, etc.), alkylthio group (methylthio group, carboxymethylthio group, sulfoethylthio group, etc.), amino group (unsubstituted amino group, dimethylamino group, N-carboxyethyl-N-methylamino group, etc.) )
Can be given.

Specific examples of the compound represented by formula (S) are given below.

[0032]

[Chemical 6]

[0033]

[Chemical 7]

[0034]

[Chemical 8]

The content of sulfinic acid used in the present invention is 0.001 to 1.0 mol / liter, preferably 0.002 to 0.2 mol / liter.

In the present invention, the pH of the bleach-fixing solution is
4.5 to 7.5 is suitable, and preferably 5.0 to 7.
It is 0. The pH of the bleach-fix replenisher is suitably 4.0 to 7.0, preferably 4.5 to 6.5. The bleach-fixing step can be performed in the temperature range of 30 ° C to 50 ° C, preferably 35 ° C to 40 ° C. The processing time in the bleach-fixing step is 10 seconds to 2 minutes, preferably 10 seconds to 1 minute. Also, more preferably 15 seconds to 45 seconds.
Seconds. The replenishing amount of the bleach-fixing solution is 1 m ² of the light-sensitive material,
10 to 1500 ml, preferably 20 to 300 ml,
More preferably, it is 30 to 200 ml. At such low replenishment rates, the method of the present invention is particularly effective and stable,
It is preferable in that the desilvering property and the prevention of color restoration failure (prevention of leuco formation of cyan dye) can be improved.

The color developing replenisher and the color developing solution used in the present invention will be described below. The color developing solution replenisher and the color developing solution used in the present invention contain known aromatic primary amine color developing agents. A preferred example is a p-phenylenediamine derivative, and as a representative example, N, N-diethyl-p-phenylenediamine, 2-amino-5-diethylaminotoluene, 2-amino-5- (N-ethyl-N-lauryl). Amino) toluene, 4- [N-ethyl-N- (β-hydroxyethyl) amino] aniline, 2-methyl-4- [N-
Ethyl-N- (β-hydroxyethyl) amino] aniline, 2-methyl-4- [N-ethyl-N- (β-hydroxybutyl) amino] aniline, 4-amino-3-methyl-N-ethyl-N -[Β- (methanesulfonamide)
Ethyl] aniline, N- (2-amino-5-diethylaminophenylethyl) methanesulfonamide, N, N-
Dimethyl-p-phenylenediamine, 4-amino-3-
Methyl-N-ethyl-N-methoxyethylaniline, 4
Examples include -amino-3-methyl-N-ethyl-N-β-ethoxyethylaniline and 4-amino-3-methyl-N-ethyl-N-β-butoxyethylaniline. Particularly preferably 4-amino-3-methyl-N-ethyl-N- [β- (methanesulfonamido) ethyl]-
Aniline, 2-methyl-4- [N-ethyl-N- (β-
Hydroxybutyl) amino] aniline. 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 generally about 4 mmol to 50 mmol per liter of the color developing solution, but the amount of the color developing replenishing solution is preferably per 1 liter of the replenishing solution. Is about 21 millimolar to 65 millimolar, more preferably about 28 millimolar to 55 millimolar.

In the practice of the present invention, a color developing replenisher and a color developing solution containing substantially no benzyl alcohol are used in order to prevent precipitation of the replenisher and to prevent fluctuations in photographic characteristics due to fluctuations in the amount of processing. Preference is given to using. Here, the term "substantially free from" means preferably 2 ml.
/ Liter or less, more preferably 0.5 ml / liter or less of benzyl alcohol concentration, and most preferably
That is, it contains no benzyl alcohol.

In the present invention, prevention of precipitation of the replenisher and
From the viewpoint of preventing fluctuations in photographic characteristics due to fluctuations in processing amount, color development replenishers and color developers which are substantially free of sulfite and hydroxylamine are preferred. Particularly, in the absence of sulfite and hydroxylamine, the precipitation of the replenisher is significantly improved. Here, the term "substantially free from" means 4 mmol or less per liter of the color developing replenisher or the color developing solution, more preferably 2 mmol or less, and it is particularly preferable not to contain any.

In the present invention, it is preferable to contain a compound represented by the following general formula (I) from the viewpoints of preservability and prevention of fluctuations in photographic characteristics associated with fluctuations in processing amount. In particular, the presence of the compound of the general formula (I) significantly improves the preservability. General formula (I)

[0041]

[Chemical 9]

In the formula, R ¹ and R ² 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 ₁ and R ₂ 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, oxygen atoms, nitrogen atoms, sulfur atoms and the like, and may be saturated or unsaturated. It is preferable that R ¹ and R ² are an alkyl group or an alkenyl group, and the carbon atom number is preferably 1 to 10, and particularly preferably 1 to 5. Examples of the nitrogen-containing heterocycle formed by connecting R ₁ and R ₂ include a piperidyl group, a pyrrolidylyl group, an N-alkylpiperazyl group, a morpholyl group, an indolinyl group, and a benztriazole group. Specific examples of the compound represented by formula (I) in the present invention are shown below, but the present invention is not limited thereto. The addition amount of the following compounds to the color developing solution and the color developing replenishing solution is 0.005 mol / liter to 0.5.
It is desirable to add it at a concentration of mol / liter, preferably 0.03 mol / liter to 0.1 mol / liter.

[0043]

[Chemical 10]

[0044]

[Chemical 11]

In the present invention, as a preservative, other organic preservatives can be added, if necessary, in addition to the compound of the general formula (I). 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 the oxidation of the color developing agent by the air, among them, 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 organic preservatives. They are,
JP-B-48-30496, JP-A-52-143020
No. 63-4235, No. 63-30845, No. 6
3-21647, 63-46455, 63-5
No. 3551, No. 63-43140, No. 63-5665.
No. 4, No. 63-58346, No. 63-43138,
63-146041, 63-44657, 6
3-44656, U.S. Pat. No. 3,615,503,
No. 2,494,903, JP-A Nos. 1-97953, 1-186939, 1-186940, 1-1.
No. 87557, No. 2-306244 and the like. Other preservatives include various metals described in JP-A-57-44148 and 57-53749, salicylic acids described in JP-A-59-180588, and JP-A-63.
-239447, JP-A-63-128340, JP-A-1-186939 and JP-A-1-187557, alkanol amines described in JP-A-54-3532, JP-A-56 -94349 described polyethylene imines, US Pat. No. 3,746,544
The aromatic polyhydroxy compounds described in No. etc. may be used if necessary. In particular, addition of alkanolamines such as triethanolamine is preferable.

In the present invention, the addition of an aromatic polyhydroxy compound is particularly preferable from the viewpoint of improving the stability of the developing solution. Generally, an aromatic polyhydroxy compound is a compound having on the aromatic ring at least two hydroxy groups located in the ortho position relative to each other. Also preferably, these polyhydroxy compounds are compounds having at least two hydroxy groups located in the ortho position relative to each other on the aromatic ring and having no exocyclic unsaturation. The wide range of aromatic polyhydroxy compounds in the present invention include compounds represented by the following general formula (II) such as benzene and naphthalene compounds. General formula (II)

[0047]

[Chemical 12]

Z represents an atomic group necessary for completing the aromatic nucleus of benzene or naphthalene. In addition to hydroxy substituents, the above compounds may be substituted with groups or atoms such as, for example, sulfo groups, carboxy groups or halogen atoms. Typical examples of the aromatic polyhydroxy compound preferably used in the present invention are as follows. II-1 Pyrocatechol II-2 4,5-dihydroxy-m-benzene-1,3
-Disulfonic acid II-34,5-dihydroxy-m-benzene-1,3
-Disulfonic acid / disodium salt II-4 Tetrabromopyrocatechol II-5 Pyrogallol II-6 5,6-Dihydroxy-1,2,4-benzenetrisulfonic acid sodium salt II-7 Gallic acid II-8 Methyl gallate II -9 Propyl gallate II-10 2,3-dihydroxynaphthalene-6-sulfonic acid II-11 2,3,8-trihydroxynaphthalene-6-
Sulfonic acid These compounds are present in the color developing solution and the color developing replenishing solution, and the addition amount thereof is 0.00005 to 0.1 mol, and generally 0.0002 per liter of the developing solution.
~ 0.04 mol, preferably 0.0002-0.004
It is a mole.

The color developing solution used in the present invention preferably has a pH of 9 to 12, more preferably 9 to 11.0, and the color developing solution contains compounds of other known developing solution components. be able to. The color developing replenisher used in the present invention preferably has a pH of 11 to 14, and more preferably 11.5-13.5. In particular, from the viewpoint of preventing precipitation of the replenisher and reducing the replenishment amount, the pH is 12.0 to 13.
It is particularly preferably 0. In order to maintain the above pH, it is preferable to use various buffers. Examples of the buffer include carbonate, phosphate, borate, tetraborate, hydroxybenzoate, glycyl salt, N, N-dimethylglycine salt, leucine salt, norleucine salt, guanine salt, 3,
4-dihydroxyphenylalanine salt, alanine salt, aminobutyric acid salt, 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, tetraborates, and hydroxybenzoates have excellent solubility and buffering ability in the high pH range of pH 9.0 or higher, and even when added to color developers, they adversely affect photographic performance. It is particularly preferable to use these buffers, because they have the advantages of being free from (fogging, etc.) and being 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. , Potassium borate, sodium tetraborate (borax),
Potassium tetraborate, sodium o-hydroxybenzoate (sodium salicylate), potassium o-hydroxybenzoate, sodium 5-sulfo-2-hydroxybenzoate (sodium 5-sulfosalicylate), 5-sulfo-
Examples thereof include potassium 2-hydroxybenzoate (potassium 5-sulfosalicylate). The amount of the buffer added to the color developing solution and the color developing replenishing solution is 0.1.
It is preferably at least mol / liter, particularly 0.1
It is particularly preferable that it is from mol / liter to 0.4 mol / liter.

In the present invention, various chelating agents can be used in the color developing solution as an agent for preventing the precipitation of calcium or magnesium or for improving the stability of the color developing solution. For example, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, ethylenediaminetetraacetic acid, N,
N, N-trimethylenephosphonic acid, ethylenediamine-
N, N, N ', N'-tetramethylenephosphonic acid, trans-cyclohexanediaminetetraacetic acid, 1,2-diaminopropanetetraacetic acid, glycol ether diaminetetraacetic acid, ethylenediamine orthohydroxyphenylacetic acid, 2-phosphonobutane-1,2. , 4-tricarboxylic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, N, N'-
Bis (2-hydroxybenzyl) ethylenediamine-
Examples thereof include N, N'-diacetic acid and hydroxyethyliminodiacetic acid. Two or more of these chelating agents may be used in combination, if necessary. The amount of these chelating agents added may be an amount sufficient to block the metal ions in the color developing solution. For example, it is about 0.1 g to 10 g per liter.

If desired, any development accelerator can be added to the color developing solution. As a development accelerator, Japanese Patent Publication No. 37
-16088, 37-5987, 38-782.
No. 6, No. 44-12380, No. 45-9015 and U.S. Pat. No. 3,318,247, and the like, thioether compounds, JP-A Nos. 52-49829 and 52-49829.
P-phenylenediamine compounds represented by JP-A-15554, JP-A-50-137726, and JP-B-44-3.
No. 0074, JP-A Nos. 56-156826 and 52-
Quaternary ammonium salts represented by U.S. Pat. No. 4,434,29, US Pat. Nos. 2,494,903 and 3,128,182.
No. 4,230,796, 3,253,919
No. 4, Japanese Patent Publication No. 41-11431, US Pat. No. 2,48
2,546, 2,596,926 and 3,58
Amine compounds described in 2,346, etc., JP-B-37-
16088, 42-25201, U.S. Pat.
128,183, Japanese Patent Publication Nos. 41-11431, 42
-23883 and U.S. Pat. No. 3,532,501 and the like, polyalkylene oxides, other 1-phenyl-3-pyrazolidones, imidazoles, and the like can be added as necessary. The benzyl alcohol is as described above.

In the present invention, any antifoggant can be added, if desired. 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 antifoggants include bendtriazole, 6-nitrobenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chloro-benzotriazole, 2-thiazolyl-benzimidazole, 2 Typical examples include nitrogen-containing heterocyclic compounds such as -thiazolylmethyl-benzimidazole, indazole, hydroxyazaindolizine and adenine. In the present invention, the chloride ion concentration in the color developer is 5 × 1.
It is preferably 0 ^{−2 to} 2 × 10 ⁻¹ mol / liter from the viewpoint of preventing photographic characteristic fluctuation. More preferably 6 × 1
0 ^{-2 to} 1.5 x 10 ^-1 mol / liter, especially 8 x
It is 10 ^{−2 to} 1.3 × 10 ⁻¹ mol / liter. Also,
In the present invention, the bromide ion concentration in the color developer is 1 × 10 ⁻⁴ to 4 × 10 ⁻⁴ mol / liter,
It is preferable in terms of preventing photographic characteristic fluctuation. It is more preferably 1.2 × 10 ^{−4 to} 3.8 × 10 ⁻² mol / liter, and particularly preferably 1.5 × 10 ^{−4 to} 3.5 × 10 ⁻⁴ mol / liter. Further, most preferably, the chloride ion and the bromide ion having the above concentrations coexist.

In the present invention, the color developing solution and the color developing replenishing solution may contain a fluorescent whitening agent, if necessary. Fluorescent brighteners include 4,4'-diamino-
2,2'-disulfostilbene compounds are preferred. Among them, the compound represented by the following general formula (SR) is particularly preferable in terms of solubility in the replenisher, prevention of replenisher precipitation, and reduction of stain of the photosensitive material after processing. General formula (SR)

[0055]

[Chemical 13]

In the general formula [SR], L ¹ and L ² may be the same or different, --OR ¹ or --NR ² R
³ (R ¹ , R ² and R ³ are each a hydrogen atom or an alkyl group) and satisfy at least one of the following conditions. Four substituents L ¹ and L in the general formula [SR]
² has a total of 4 or more substituents selected from the general formula [A] group. Four substituents L ¹ and L in the general formula [SR]
² has a total of two substituents selected from the general formula [A] group, and has a total of two or more substituents selected from the general formula [B] group.

[0057]

[Chemical 14]

In the general formula [A] group, X is a halogen atom and R is
Represents an alkyl group. In the general formulas [SR] and [A], M represents a hydrogen atom, an alkaline earth metal, ammonium or pyridinium. The diaminostilbene-based optical brightening agent of the general formula [SR] used in the present invention has a specific structure in which L ¹ and L ² are represented by the atomic groups shown below. Is not limited to these.

[0059]

[Table 1]

[0060]

[Table 2]

[0061]

[Table 3]

[0062]

[Table 4]

[0063]

[Table 5]

[0064]

[Table 6]

The compound of the general formula [SR] is effective when used alone or in combination with a plurality of other diaminostilbene compounds. Is it a compound of [SR],
Alternatively, a diaminostilbene compound represented by the following general formula [SR-c] is preferable.

[0066]

[Chemical 15]

In the general formula [SR-c], L ⁵ , L ⁶ ,
L ⁷ and L ⁸ are represented by —OR ⁸ or —NR ⁹ R ¹⁰ and may be the same or different. Here, R ⁸ , R ⁹ and R ¹⁰ represent a hydrogen atom, an alkyl group, or an alkyl group having a substituent. General formula [SR-
Specific examples of the compound represented by c] include the compounds shown in Table 2.

[0068]

[Table 7]

As the fluorescent whitening agent which can be used in combination with the compound of the general formula [SR], a commercially available diaminostilbene type fluorescent whitening agent may be used. Examples of commercially available compounds include Dyeing Note 19th Edition (Color Sensha Co., Ltd.); 165-P. 168
And among the products listed here
Whitex RP or Whitex BRF liq. Is preferred.

If desired, various surfactants can be added. Specific examples of the surfactant include the general formulas (I) and (II) described in JP-A-4-195037.
Compound of formula (I) described in JP-A-4-81750.
To (X) compounds and the like can be mentioned. Further, it is preferable that the surface tension of the color developing solution and the color developing replenishing solution is adjusted to 20 to 60 dyue / cm by adding the above compound. The processing temperature of the color developer applicable to the present invention is 20 to 50 ° C, preferably 30 to 45 ° C. The processing time is 20 seconds to 5 minutes, preferably 30 seconds to 2 minutes.

In the present invention, the replenishing amount of the color developing solution is suitably 20 to 1000 ml, preferably 30 to 200 ml, and more preferably 35 to 80 ml per 1 m ² of the light-sensitive material. In the present invention, like the bleach-fixing replenisher, it is particularly preferable to coat the surface of the color developing replenisher with the floating fluid of the present invention from the viewpoint of improving stability.

After the processing step having fixing ability, usually,
Perform a washing process. After processing with a processing solution with fixing ability,
It is also possible to use a simple treatment method in which a stabilizing treatment using the stabilizing solution of the present invention is carried out without substantially washing with water. The replenishing amount in the water washing step or the stabilizing step is 3 to 50 times, preferably 3 to 30 times, the amount carried in from the previous bath per unit area of the light-sensitive material. It is more preferably 3 to 10 times. When the stabilization treatment is performed after washing with water, the method of the present invention is effective in a treatment system in which the stabilization step of the final step is 3 to 50 times. The replenishment may be performed continuously or intermittently. The liquid used in the washing and / or stabilizing step can be further used in the previous step. As an example of this, it is possible to reduce the amount of waste liquid by reducing the overflow of washing water into a bleach-fixing bath, which is the pre-bath, by supplementing the bleach-fixing bath with a concentrated liquid by reducing the overflow of the washing water by a multi-stage countercurrent system. The amount of rinsing water in the rinsing process depends on the characteristics of the photosensitive material (for example, depending on the material used such as couplers) and application, the rinsing water temperature, the number of rinsing tanks (the number of stages), the replenishment method such as countercurrent and forward flow, and various other conditions. Can be set to a range. Generally, the number of stages is preferably 2 to 6 in the multi-stage countercurrent system,
Especially, 2 to 4 are preferable.

According to the multi-stage countercurrent system, the amount of washing water can be greatly reduced, and, for example, 0.5 liter / m ^{2 of the} light-sensitive material can be used.
Although it can be 1 liter or less, the increase in the residence time of water in the tank causes problems such as bacteria breeding and the produced suspended matter adhering to the photosensitive material. As a solution to such a problem, the method of reducing calcium and magnesium described in JP-A-62-288838 can be used very effectively. It is also preferable to use water that has been sterilized by using a halogen, an ultraviolet germicidal lamp, or an ozone generator.

Further, it is preferred that the washing water and the stabilizing solution contain various antibacterial agents and antifungal agents for preventing the generation of water stains and the mold generated in the processed light-sensitive material. Examples of these antibacterial agents and antifungal agents include thiazolylbenzimidazole compounds as shown in JP-A-57-157244 and 58-105145, and JP-A-57-8542. Isothiazolone compounds, chlorophenol compounds such as trichlorophenol, bromophenol compounds, organotin and organozinc compounds, acid amide compounds,
Diazine and triazine compounds, thiourea compounds,
Benzotriazole compounds, alkylguanidine compounds, quaternary ammonium salts represented by benzalkonium chloride, antibiotics represented by penicillin, Journal Antibacterial &
Antifungus Agent (J.Antibact.Antif
ung.Agents) Vol 1. No. 5, p.207-223 (19
83) Hiroshi Horiguchi, "Antibacterial and Antifungal Chemistry" (1986) Sankyo Publishing, edited by the Sanitary Engineering Society, "Microbial sterilization, sterilization and antifungal technology"
(1982) Industrial Technology Association, general antibacterial agents and the like described in "Encyclopedia of Antibacterial and Antifungal Agents" (1986) edited by Japan Society for Antibacterial and Antifungal Agents. You may use these 2 or more types together. Further, various bactericides described in JP-A-48-83820 can also be used.

The washing water and the stabilizing solution preferably contain various surfactants in order to prevent unevenness of water droplets when the photosensitive material after processing is dried. As these surfactants, polyethylene glycol type nonionic surfactants,
Polyhydric alcohol type nonionic surfactant, alkylbenzene sulfonate type anionic surfactant, higher alcohol sulfate ester salt type anionic surfactant, alkylnaphthalene sulfonate type anionic surfactant, quaternary ammonium salt Type cationic surfactants, amine salt type cationic surfactants, amino salt type amphoteric surfactants, betaine type amphoteric surfactants are preferable, but nonionic surfactants are preferably used, especially alkylphenol ethylene oxide addition The thing is preferable. Octyl, nonyl, dodecyl and dinonylphenol are particularly preferable as the alkylphenol, and 8 to 14 are particularly preferable as the number of moles of ethylene oxide added. Further, it is also preferable to use a silicon-based surfactant having a high defoaming effect.

Further, it is preferable that the washing water and the stabilizing solution contain various chelating agents. Preferred chelating agents include aminopolycarboxylic acids such as ethylenediaminetetraacetic acid and diethylenetriaminepentaacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, ethylenediaminetetraacetic acid and diethylenetriamine-N, N, N ', N'-tetramethylene. Examples thereof include organic phosphonic acids such as phosphonic acid, and hydrolysates of maleic anhydride polymers described in European Patent 345172A1.

In the stabilizing solution, compounds that stabilize the dye image, such as formalin, hexamethylenetetramine and its derivatives, hexahydrotriazine and its derivatives, N-methylol compounds such as dimethylolurea and N-methylolpyrazole, and organic compounds are used. Acids, pH buffers, etc. are included. The addition amount of these compounds is preferably 0.001 to 0.02 mol per liter of the stabilizing solution, but the lower the free formaldehyde concentration in the stabilizing solution is, the less the formaldehyde gas is scattered, which is preferable. From this point of view, examples of the dye image stabilizer include hexamethylenetetramine and N-methylolpyrazole.
N-methylolazoles described in 318644, N,
Azolylmethylamines described in Japanese Patent Application No. 3-142708 such as N'-bis (1,2,4-triazol-1-yl) piperazine are preferable. In addition, if necessary, ammonium compounds such as ammonium chloride and ammonium sulfite, metal compounds such as Bi and Al, optical brighteners,
It is also preferable to contain a hardening agent, an alkanolamine described in U.S. Pat. No. 4,786,583, and a preservative that can be contained in the fixing solution or the bleach-fixing solution. Among these, the sulfinic acid compounds described in JP-A No. 1-231051 (for example, benzenesulfinic acid, toluenesulfinic acid, or salts thereof such as sodium and potassium) are preferable, and the addition amount of these is a stabilizing solution. 1
1 × 10 ⁻⁵ × 1 × 10 ⁻³ mol per liter is preferable, and 3 × 10 ^{−5 to} 5 × 10 ⁻⁴ mol is particularly preferable.

The replenishing amount in the washing or stabilizing step is 50 to 2000 ml, preferably 100 to 1 per 1 m ² of the light-sensitive material.
It is 000 ml.

As a means of reducing the replenishment amount without impairing the stability of the dye image, the method of reverse osmosis treatment using a reverse osmosis membrane described in JP-A-3-55542 can be particularly effectively used. The treatment of a washing solution and / or a stabilizing solution with a reverse osmosis membrane means that the solution in at least one tank constituting the washing and / or stabilizing step is brought into contact with the reverse osmosis membrane, (Liquid) is returned to the tank constituting the washing and / or stabilizing step. The multi-stage countercurrent washing and / or stabilizing process preferably comprises 2 to 6 tanks, more preferably 3 to 5 tanks, and particularly preferably 4 to 5 tanks. All of these constituent tanks may be washing baths, or all may be stabilizing baths. When the washing and / or stabilizing process of the multi-stage countercurrent method is three or more tanks, the tank for installing the reverse osmosis membrane is the tank after the second tank and one tank before the final tank. It is preferable. In this case, it is preferable that the permeated liquid that has passed through the reverse osmosis membrane and is purified is returned to the tank located after the reverse osmosis membrane installation tank, and the concentrated liquid is returned to the tank in which the reverse osmosis membrane is installed.
In the present invention, it is particularly preferable that the multi-stage countercurrent washing and / or stabilizing process comprises four or more tanks, and a reverse osmosis membrane is installed in the third tank or later. There are various reverse osmosis membranes such as a high pressure reverse osmosis membrane, an intermediate pressure reverse osmosis membrane, and a low pressure reverse osmosis membrane, but a low pressure reverse osmosis membrane is preferable.
More specifically, an aqueous solution containing 2000 ppm of Nacl is added to 25
A reverse osmosis membrane having a NaCl exclusion rate of 30 to 90% in the permeate when subjected to a reverse osmosis membrane treatment under conditions of ° C and a pressure of 5 kg / cm ² is preferable. By using such a loose reverse osmosis membrane, the amount of the permeated liquid is large even at a low pressure, and EDTA-Fe, which is the cause of the stain, can be sufficiently removed. These reverse osmosis membranes include a skin layer that controls the membrane performance such as the amount of permeated water and the rejection rate, and a support layer that supports the same, and there are asymmetric membranes made of the same material and composite membranes made of different materials. A synthetic composite membrane is preferably used in terms of exclusion rate, permeated water amount, and durability against EDTA-Fe. Details of the synthetic composite membrane are described in Kagaku Kogyo's separate volume Kagaku Kogyo 29-7 “Development and Practical Use of Advanced Separation Technology”, pages 156 to 172. As a specific example of the synthetic composite film, DRA- manufactured by Daicel Chemical Industries, Ltd.
40, DRA-80, DRA-89 and SU-2 made by Toray
00, SU-210, SU-220 and the like. The feed pressure of the processing liquid supplied to the reverse osmosis membrane is 2 to 20 kg / cm.
² is preferable, more preferably 3 to 15 kg / cm ² , still more preferably 3 to 10 kg / cm ² , and most preferably 3 to 6 kg.
/ Cm ² . The permeated liquid supply amount (the amount of liquid that permeates the reverse osmosis membrane and is purified, and is supplied to the treatment tank located after the reverse osmosis membrane installation tank) is defined as F, and the concentrated liquid amount (the reverse osmosis membrane concentrated by the reverse osmosis membrane is used. When the amount of liquid returned to the installation tank is C and the fresh liquid replenishment amount is R, the permeate supply amount F is preferably not less than the fresh liquid replenishment amount R, more preferably F is 2 to 2 of R.
It is 00 times, more preferably 5 to 150 times, and particularly preferably 10 to 100 times. Further, the concentrated liquid amount C is preferably equal to or more than the permeated liquid supply amount F, more preferably C is 2 to 100 times F, and further preferably 3 to.
It is 50 times, and particularly preferably 5 to 30 times. Here, the flow rates of F, C and R in the above all mean the flow rate per day. In the method of reverse osmosis treatment using a reverse osmosis membrane, the replenishing amount in the washing or stabilizing step may be 200 ml or less per 1 m ² of the light-sensitive material,
The amount is more preferably 30 to 200 ml, and still more preferably 50 to 150 ml, per m ² of the light-sensitive material. The washing and stabilizing solutions are usually used in a pH range of 4 to 10, but preferably 6 to 9. In addition, the treatment temperature for washing and stabilizing solution is 30-
45 ° C is preferred. The processing time is usually 10 seconds to 2
Minutes, especially 10 to 60 seconds, are preferred.

In order to further reduce the amount of the replenisher solution for environmental protection, it is also preferable to use various regeneration methods in combination. Regeneration may be performed while circulating the processing solution in the automatic processor, or after removing the processing solution from the processing tank, performing appropriate recycling processing and returning it to the processing tank as a replenishing solution again. Is also good. In particular, the developer can be regenerated and used. Regeneration of the developing solution means that the used developing solution is subjected to anion exchange resin or electrodialysis, or the processing solution called a regenerant is added to increase the activity of the developing solution and to use it again as a processing solution. . In this case, the regeneration rate (ratio of the overflow solution in the replenisher) is preferably 50% or more, particularly preferably 70% or more.
As a process using the regenerating of the developing solution, the replenishing solution is used after regenerating the overflow solution of the developing solution. As a method of reproduction,
It is preferable to use an anion exchange resin. Particularly preferred anion exchange resin compositions and resin regeneration methods include those described in DIAION MANUAL (I) (14th edition, 1986) issued by Mitsubishi Kasei Co., Ltd. Further, among the anion exchange resins, resins having the compositions described in JP-A-2-952 and 1-281152 are preferable. In addition, Japanese Patent Laid-Open No. 3-17415
As in the method described in No. 4, it is most preferable in terms of simplicity that the overflow solution is not subjected to any treatment such as anion exchange resin or electrodialysis, and only the regenerant is added to form a replenisher solution.

Since the metal chelate bleaching agent in the bleaching solution and / or the bleach-fixing solution becomes a reducing state with the bleaching treatment, the bleaching solution and / or the bleach-fixing solution should be continuously regenerated in cooperation with the treatment. It is preferable to take. In particular,
It is preferable to blow air into the bleaching solution and / or the bleach-fixing solution with an air pump to reoxidize the metal chelate in a reduced state by oxygen, so-called aeration. In addition, it can be regenerated by adding an oxidizing agent such as hydrogen peroxide, persulfate or bromate. The fixing solution and the bleach-fixing solution are regenerated by electrolytically reducing accumulated silver ions. In addition, it is also preferable to remove accumulated halogen ions with an anion exchange resin in order to maintain the fixing performance.

The bleach-fixing solution is EP-479262.
It is easy to add only the regenerant to the overflow solution as a replenisher without performing aeration or removing silver ions with an anion exchange resin like the method described in A1. Most preferred in that respect. In the present invention, the processing solution having fixing ability can be subjected to silver recovery by a known method, and a reclaimed solution subjected to such silver recovery can be used. As a silver recovery method,
Electrolysis method (described in French Patent No. 2,299,667),
Precipitation method (JP-A-52-73037, German Patent Nos. 2 and 3)
No. 31,220), an ion exchange method (JP-A-51-1)
7114, German Patent No. 2,548,237) and metal substitution method (UK Patent No. 1,353,805).
Etc. are effective. These silver recovery methods are preferable when they are carried out in-line from the tank solution because the suitability for rapid processing is further improved.

The processing method of the present invention is carried out using an automatic processor. An automatic processor which is preferable for the present invention will be described below. Areas where the color developer and color replenisher replenisher are in contact with air in the processing tank and replenisher tank (opening area)
Is preferably as small as possible. For example, when the opening ratio is a value obtained by dividing the opening area (cm ² ) by the liquid tank (cm ³ ) in the tank, the opening ratio is preferably 0.01 (cm ^-1 ) or less,
It is more preferably 005 or less, and most preferably 0.001 or less.

In the present invention, in order to carry out the processing promptly, the shorter the in-air time when the photosensitive material moves between the processing solutions, that is, the crossover time, the shorter, the better, and preferably 10 seconds or less, more preferably 7 Seconds or less, more preferably 5 seconds or less. In order to achieve the above-mentioned short-time crossover, it is preferable to use a cine type automatic developing machine in the present invention, and a leader transporting method is particularly preferable. Such a system is an automatic processor FP-56 manufactured by Fuji Photo Film Co., Ltd.
It is used for OB. The linear velocity of conveyance is preferably high, but is generally 30 cm to 30 m / min, preferably 50 cm to 10 m. As a reader and a conveying means for the photosensitive material, there are disclosed in JP-A-60-191257 and JP-A-6-191257.
0-191258 and 60-191259 are preferably belt-conveying systems. In particular, as a conveying mechanism,
It is preferable to employ each of the methods described in Japanese Patent Application Nos. 1-265794, 1-266915, and 1-266916. Further, in order to shorten the crossover time and prevent the processing liquid from being mixed, the structure of the crossover rack preferably has a mixing prevention plate described in Japanese Patent Application No. 1-265795.

It is preferable to perform so-called evaporation correction by supplying water corresponding to the evaporation of the processing liquid to each processing liquid in the present invention. Particularly, it is preferable in a color developing solution, a bleaching solution or a bleach-fixing solution. The specific method of replenishing water is not particularly limited, but among them, a monitor water tank different from the bleaching tank described in JP-A-1-254959 and 1-254960 is installed. The method of calculating the amount of evaporation of water inside, calculating the amount of evaporation of water in the bleaching tank from this evaporation amount, and replenishing the bleaching tank with water in proportion to this evaporation amount, and Japanese Patent Application No. 2-46743, 2-4
No. 7777, No. 2-47778, No. 2-47779
The evaporation correction method using a liquid level sensor and an overflow sensor described in JP-A No. 2-117792 / 1990 is preferable. The most preferable evaporation correction method is to predict and add water corresponding to the amount of evaporation.
As described in No. 3, the amount of water added is calculated by a coefficient previously obtained based on the information on the operating time, stop time and temperature control time of the automatic processor.

Further, it is necessary to devise a method for reducing the amount of evaporation, and it is required to reduce the opening area and adjust the air volume of the exhaust fan. For example, the preferable opening ratio of the color developing solution is as described above, but it is preferable to reduce the opening area of other processing solutions as well. The exhaust fan is attached to prevent condensation during temperature control,
Preferred emissions, per minute 0.1 m ³ to 1 m ^3,
Particularly preferred engine displacement, a 0.2m ³ ~0.4m ^3. Further, the drying condition of the photosensitive material also affects the evaporation of the processing liquid. The drying method is preferably a ceramic hot air heater is preferably min 4m ³ to 20 m ³ as feed air volume, particularly 6 m ³ through 10m ³ preferred. The heating prevention thermostat of the ceramic warm air heater is preferably operated by heat transfer, and the mounting position is preferably attached to the leeward or upwind side through the heat radiation fins or the heat transfer portion. The drying temperature is preferably adjusted according to the water content of the light-sensitive material to be processed, and is optimally 45 to 55 ° C for a 35 mm wide film and 55 to 65 ° C for a brownie film. A replenishing pump is used for replenishing the processing liquid, but a bellows type replenishing pump is preferable. Also,
As a method of improving replenishment accuracy, it is effective to reduce the diameter of the liquid feeding tube to the replenishment nozzle in order to prevent backflow when the pump is stopped. A preferable inner diameter is 1 to 8 mm, and a particularly preferable inner diameter is 2 to 5 mm.

Various parts materials are used in the automatic processor, but preferred materials are described below. The tank material such as the treatment tank and the temperature control tank is preferably modified PPO (modified polyphenylene oxide) or modified PPE (modified polyphenylene ether) resin. Examples of the modified PPO include "Noryl" manufactured by GE Plastics Co., Ltd., and examples of the modified PPE include "Zylon" manufactured by Asahi Kasei Kogyo Co., Ltd. and "Yupiace" manufactured by Mitsubishi Gas Chemical Company. In addition, these materials are suitable for parts that may come into contact with the processing liquid, such as processing racks and crossovers. A resin such as PVC (polyvinyl chloride), PP (polypropylene), PE (polyethylene), TPX (polymethylpentene) is suitable for the roller material of the processing section. Further, these materials can be used for other processing liquid contact portions. PE resin is also preferable as a material for the replenishment tank by blow molding. The processing parts, gears, sprockets, bearings, etc. are made of PA (polyamide), PBT (polybutylene terephthalate), UH.
Resins such as MPE (ultra high molecular weight polyethylene), PPS (polyphenylene sulfide), LCP (whole aromatic polyester resin, liquid crystal polymer) are suitable. The PA resin is a polyamide resin such as 66 nylon, 12 nylon, or 6 nylon, and those containing glass fibers, carbon fibers, etc. are strong against swelling by the treatment liquid and can be used.
Also, high molecular weight products such as MC nylon and compression molded products can be used without fiber reinforcement. Unreinforced products are suitable for UHMPE resin, and Mitsui Petrochemical Co., Ltd.'s "Lubema", "Hi-Zex Million" Sakushin Kogyo Co., Ltd. "New Light", Asahi Kasei Kogyo Co., Ltd. "Sunfine", etc. Is suitable. The molecular weight is preferably 1,000,000 or more, more preferably 1,000,000 to 50.
It is 0,000. The PPS resin is preferably reinforced with glass fiber or carbon fiber. Examples of the LCP resin include "Victrex" of ICI Japan Co., Ltd., "Econol" of Sumitomo Chemical Co., Ltd., "Zyder" of Nippon Oil Co., Ltd., "Vectra" of Polyplastics Co., Ltd., and the like. In particular, as the material of the conveyor belt, the ultra high strength polyethylene fiber and polyvinylidene fluoride resin described in Japanese Patent Application No. 2-276886 are preferable. Foamed vinyl chloride resin, foamed silicone resin, and foamed urethane resin are suitable as soft materials such as squeeze rollers. Examples of the foamed urethane resin include “Rubicel” manufactured by Toyo Polymer Co., Ltd. EPDM rubber, silicon rubber, viton rubber, and the like are preferable as the rubber material for the joints of the pipes, the joints of the agitation jet pipe, and the sealing material.

The drying time is preferably 30 seconds to 2 minutes, more preferably 40 seconds to 80 seconds. Although the continuous processing by the replenishment method has been mainly described above, in the present invention, the processing is performed without replenishing with a fixed amount of the processing liquid, and then the whole or a part of the processing liquid is replaced with a new liquid and the processing is performed again. A batch processing method for carrying out is also preferably used.

In the present invention, it is preferable to use the following automatic developing machine. Fuji Photo Film Co., Ltd. printer processor PP400, PP401B, PP54
0B, PP1040B, PP1270, PP1250
V, PP1820V, PP2600B, PP700W,
Same film processor FP230B, FP350, F
P550B, FP560B, FP20. Noritsu Koki Co., Ltd., RPV2-204, 2-206, 2-209, 2-
212, 2-404, 2-406, 2-409, 2-4
12, 2-416, 2-430, CSR3-2070,
3-24100, 3-31100, 3-44100, 3
-54100, QSS-1102V2, 1700V
2, 1501, 1401, 1602, 1701V, 17
02V, QSS-MICRO. CL-PP manufactured by Konica
1501QA, PP1721QA, PP1771VQ
A, PP1772VQA, PP801A / B, CL-N
P30QAII, CL-KP50QA, KP32QA, N
PS-103. For details of the upper processor, for example, for the printer manual PP1250V manufactured by FUJIFILM Corporation and the instruction manual (for the administrator), the first edition (012DC296A / 1992.
2.7), instruction manual (for operator) 1st edition (01
2DC291A / 1992.16), Service Manual First Edition (012DD291A / 1992.6.2)
0), parts list 2nd edition (012DE291B / 19)
92.2).

The treating agent applicable to the present invention may be supplied as a concentrated solution having a single or plural parts, or may be supplied as a dusting agent. Further, the liquid may be supplied in a used liquid state, or may be a combination of a concentrated liquid, a powder and a used liquid. The material of the refill cartridge used in the present invention is
Any material such as paper, plastic and metal can be used, but the oxygen permeability coefficient is especially 50 ml / m ^2.
・ Atm ・ day or less plastic material is preferable. still,
Oxygen permeability coefficient is "O ₂ permeation of plastic container, modern packing" (O ₂
permeation of plastic container, Modern Packing;
NJCalyan, 1968) December issue, pages 143-145. A preferred plastic material is specifically vinylidene chloride (PV
DC), nylon (NY), polyethylene (PE), polypropylene (PP), polyester (PES), ethylene-vinyl acetate copolymer (EVA), ethylene-vinyl alcohol copolymer (E
VAL), polyacrylonitrile (PAN), polyvinyl alcohol (PVA), polyethylene terephthalate (PET) and the like. In the present invention, the use of PVDC, NY, PE, EVA, EVAL and PET is preferable for the purpose of reducing oxygen permeability. These materials may be used alone and may be shaped and used, or a method of forming a film and laminating a plurality of kinds (so-called composite film) may be used.
Further, as the shape of the container, various types such as bottle type, cubic type, pillow type and the like can be used, but the present invention is a cubic type which is flexible and easy to handle and can be reduced in volume after use, and this. Structures similar to are particularly preferred. When used as a composite film, the structures shown below are particularly preferable, but not limited thereto. PE / EVAL / PE, PE / aluminum foil / PE, NY / PE / NY, NY / PE / E
VAL, PE / NY / PE / WVAL / PE, PE / N
Y / PE / PE / PE / NY / PE, PE / SiO ₂ film / PE, PE / PVDC / PE, PE / NY / aluminum foil / PE, PE / PP / aluminum foil / PE, N
Y / PE / PVDC / NY, NY / EVAL / PE / E
VAL / NY, NY / PE / EVAL / NY, NY / P
E / PVDC / NY / EVAL / PE, PP / EVAL
/ PE, PP / EVAL / PP, NY / EVAL / P
E, NY / aluminum foil / PE, paper / aluminum foil / PE, paper / PE / aluminum foil / PE, PE / PV
DC / NY / PE, NY / PE / aluminum foil / P
E, PET / EVAL / PE, PET / aluminum foil / PE, PET / aluminum foil / PET / PE,

The thickness of the above composite film is about 5 to 1500 microns, preferably about 10 to 1000 microns. The content of the finished container is 100 to 20 liters, preferably about 5.00 to 10 liters. The above container (cartridge)
May have a cardboard or plastic outer box,
It may be formed integrally with the outer box. Various processing liquids can be filled in the cartridge of the present invention. For example, a color developing solution, a black and white developing solution, a bleaching solution, an adjusting solution, an inversion solution, a fixing solution, a bleach-fixing solution, a stabilizing solution and the like can be mentioned. It is preferred to use developers, fixers and bleach-fixers.

As conventional processing liquid containers, high-density polyethylene (HDPE), polyvinyl chloride resin (PV
C), a single-layer material such as polyethylene terephthalate (PET), or a rigid container using a multilayer material such as nylon / polyethylene (NY / PE) can be used. Further, it is possible to use a liquid container which has flexibility so that it is easy to reduce the volume of the container, that is, to reduce the required space after the contents are discharged and emptied. In the present invention, it is preferable to use the flexible container.
As a specific example of the flexible container, a liquid container opened and closed by a lid member having a hard mouth portion projecting upward from the flexible container body, the container body and the mouth portion being opened and closed. Is integrally molded with a container having a bellows portion at least in part in the height direction of the container body (FIG.
2) can be given.

The flexible container having the bellows portion will be described below. The container shape has a bellows portion, and has a horizontal cross section of a square shape, for example, a substantially square shape (FIG. 1), a substantially hexagonal shape, a substantially octagonal shape, or a round shape (FIG. 2), an elliptical shape, etc. . The substantially square shape or the substantially hexagonal shape is preferable in that the required space is reduced in the presence of the contents. As for the number of bellows parts (uneven parts), the number of convex parts is preferably 2 to 20, more preferably 3 to 10, and particularly preferably 4 to 8. The degree of irregularity of the bellows portion is not particularly limited, but the outer peripheral dimension of the concave portion is 85% or less, preferably 40 to 75%, more preferably 50 to 75% with respect to the outer peripheral dimension of the convex portion. The ratio of the total height of the container body with the bellows part completely compressed to the total height of the container body before the contraction of the bellows part is preferably 50% or less, more preferably 40% or less, and particularly preferably 10 to 10%.
30%. This ratio is preferably 10% or more in terms of manufacturing design.

The liquid container can have a necessary gas barrier property by changing the materials and raw materials used. For example, when a high oxygen barrier property is required such as in a developing solution, low density polyethylene / polyvinyl alcohol, ethylene copolymer / low density polyethylene (LD
PE / EVOH / LDPE) three-layer structure, low-density polyethylene / nylon (LDPE / NY) layer structure mainly composed of low-density polyethylene, and gas barrier property of 25 ml / m ² · day ・ atm (20 ℃
65%) or less, preferably 0.5 to 10 ml / m ² · day
・ It can be set to be atm (20 ° C 65%). For example, when oxygen barrier properties are not required, such as in bleaching solutions, low density polyethylene (LDPE) alone or ethylene / vinyl acetate copolymer resin (EVA)
Can be formed by using. Here, the low-density polyethylene has a density of 0.940 g / cc or less, preferably 0.90 to 0.94 g / cc, and more preferably 0.905.
It is possible to use one having a content of up to 0.925 g / cc. In this case, the gas barrier property is 50 ml / m ² · day · atm (20 ° C
65%) or more, for example 100 to 5000 ml / m ² · day
・ Atm (65% at 20 ° C) can be used. The average thickness of the container mouth portion, the flange portion and the vicinity thereof is preferably 1 to 4 mm, more preferably 1 to 3 mm, and particularly preferably 1.2 to 2.5 mm. The thickness is preferably 0.1 to 1.5 mm, more preferably 0.2 to 1.0 mm, particularly preferably 0.3 to 0.7 mm, and the difference between the two is preferably 0.2 mm. More preferably, it is about 0.5 mm.

The ratio of the surface area (cm ² ) of the container to the internal volume (cm ³ ) of the container increases due to the bellows structure, but it is preferably 0.3 to 1.5 cm ^-1 , more preferably 0.4 to 1.5 cm ^-1 .
1.2 cm ^-1, it is particularly preferably 0.5 to 1.0 cm ^-1. When filling the above-mentioned container with liquid, it is preferable that the head space (the space of the space without the processing liquid in the upper part of the container) is small in terms of improving the liquid stability, but if the head space is too small, during filling or use Liquid overflow easily occurs. The liquid filling rate in the container is preferably 65 to 95.
%, More preferably 70 to 90%.

It is preferable that the cap or inner stopper of the container is made of the same material as that of the container body, since it is easy to sort the container for recycling after use. By changing the material and the raw material, it is possible to provide the necessary gas barrier property in the same manner as the main body described above. The internal volume of the container is not particularly limited, but is preferably 50 ml to 5 liters from the viewpoint of handleability. Specific examples of the flexible processing liquid containers A to D having the bellows part will be given below.

Container name Container A Container B type Approximate square shape (Fig.-1) Approximately round shape (Fig.-2) Outer circumference of convex part of bellows part (cm) 24cm 24cm Outer part of concave part (cm) 16cm 16cm Outer circumference of concave / outer circumference of convex (%) 67% 67% Height before shrinking bellows (cm) 18cm 18cm Height after shrinking 〃 (cm) 4cm 4cm Reduction rate of height due to bellows shrinkage 22% 22% Contents (ml) 580ml 580ml Filling amount (ml) 500ml 500ml Filling rate (%) 86% 86% Container body material LDPE (density 0.91g / cc) LDPE (density 0.91g / cc) / EVOH / LDPE (density) 0.91g / cc) Cap and inner plug material 〃 〃 Oxygen permeability (ml / m ²・ day ・ atm (20 ℃ 65%)) 100 1.0 Body thickness (mm) 0.5 0.5 Container surface area (cm ² ) 520 505

Container name Container C Container D type Approximate square shape (Fig.-1) Approximate square shape (Fig.1) Outer circumference of the convex part of the bellows part (cm) 35cm 35cm Outer part of the concave part (cm) 24cm 24cm Outer circumference of concave / convex area (%) 67% 67% Height before shrinking bellows (cm) 31cm 35cm Height after shrinking 〃 (cm) 7cm 8cm Reduction rate of height due to bellows shrinkage 23% 23% Content (ml) 2300ml 2900ml Filling amount (ml) 2000ml 2500ml Filling ratio (%) 86% 86% Container body material LDPE (density 0.91g / cc) LDPE (density 0.91g / cc) / EVOH / LDPE (density) 0.91g / cc) Cap and inner plug material 〃 〃 Oxygen permeability (ml / m ²・ day ・ atm (20 ℃ 65%)) 80 0.9 Body wall thickness (mm) 0.7 0.6 Container surface area (cm ² ) 1900 1940

The present invention can be applied to any photosensitive material. The silver halide emulsion and other materials (additives, etc.) and photographic constituent layers (layer arrangement, etc.) applied in the present invention, and the processing method and processing additive applied for processing the light-sensitive material are The following patent publications, particularly European Patent EP 0,355,660A2 (Japanese Patent Application No.
Those described in No. 107011) are preferably used.

[0100]

[Table 8]

[0101]

[Table 9]

[0102]

[Table 10]

[0103]

[Table 11]

[0104]

[Table 12]

As the magenta coupler, it is particularly preferable to use a pyrazolotriazole type magenta coupler. Preferred specific examples of the pyrazolotriazole type magenta coupler are shown below.

[0106]

[Chemical 16]

[0107]

[Chemical 17]

[0108]

[Chemical 18]

[0109]

[Chemical 19]

Further, as a cyan coupler, JP-A-2-
In addition to the diphenylimidazole-based cyan coupler described in 33144, European Patent EP 0,333,185A2
3-Hydroxypyridine cyan couplers (especially the couplers (42) listed as specific examples, which are 4-equivalent couplers with a chlorine leaving group to make them 2-equivalent, couplers (6) and (9) Is particularly preferable) and cyclic active methylene cyan couplers described in JP-A-64-32260 (coupler examples 3, 8, and 34 listed as specific examples are particularly preferable) are also preferably used.

As the silver halide used in the present invention, silver chloride, silver bromide, silver chlorobromide, silver iodochlorobromide, silver iodobromide and the like can be used, but especially for the purpose of rapid processing. It is preferable to use a silver chlorobromide or silver chloride emulsion having a silver chloride content of substantially 90 mol% or more, further 95% or more, and particularly 98% or more, which does not substantially contain silver iodide. The light-sensitive material used in the method of the present invention is particularly preferable as a color light-sensitive material for high silver chloride type printing (for example, color paper).

Further, in the light-sensitive material according to the present invention, a hydrophilic colloid layer is added to the photosensitive colloid layer for the purpose of improving the sharpness of an image, etc., in EP No. 0,337,490A2 No.
Dyes which can be decolorized by treatment (among others, oxonol dyes) described on page 76 are added so that the optical reflection density at 680 nm of the light-sensitive material becomes 0.70 or more, or the water-resistant resin layer of the support. 12% by weight or more (more preferably 14% by weight or more) of titanium oxide surface-treated with a dihydric to tetrahydric alcohol (eg, trimethylolethane)
It is preferably contained. Further, the light-sensitive material according to the present invention includes a coupler and a European Patent EP 0,277,58.
It is preferable to use a color image storage improving compound as described in 9A2. In particular, it is preferably used in combination with a pyrazoloazole coupler.

That is, the compound (F) and // which chemically bond with the aromatic amine developing agent remaining after the color development processing to form a chemically inactive and substantially colorless compound.
Alternatively, the compound (G) which chemically bonds with the oxidation product of the aromatic amine color developing agent remaining after the color developing treatment to form a chemically inactive and substantially colorless compound is used simultaneously or alone. However, for example, it is preferable to prevent the occurrence of stains and other side effects due to the formation of a coloring dye due to the reaction of the coupler with the color developing agent remaining in the film or its oxidant during storage after processing. Further, in the light-sensitive material according to the present invention, in order to prevent various molds and bacteria which propagate in the hydrophilic colloid layer and deteriorate the image, JP-A-63-271 is used.
It is preferable to add an antifungal agent as described in No. 247.

In the present invention, the swelling degree of the photographic layer of the silver halide color light-sensitive material is 1.1 to 3.0,
It is particularly preferable in that the adhesion of the color light-sensitive material after processing is improved. The lubricity of the present invention means a value obtained by dividing the film thickness of the photographic layer after dipping the color light-sensitive material in distilled water at 33 ° C. for 2 minutes by the film thickness of the dried photographic layer. More preferably, it is 1.3 to 2.7. Dry photographic layer thickness is 5
.About.25 micron is preferable, and more preferably 7 to 20 micron.

The photographic layer means a hydrophilic colloid group layer including at least one photosensitive silver halide emulsion layer and having a water-permeable relationship with this layer. The back layer provided on the opposite side of the support from the photographic photosensitive layer is not included. The photographic layer is usually formed of a plurality of layers involved in photographic image formation, and in addition to the silver halide emulsion layer, an intermediate layer, a filter layer, an antihalation layer, a protective layer and the like are included.

Any method may be used to adjust the swelling degree within the scope of the present invention. For example, the amount and kind of gelatin used in the photographic film, the amount and kind of hardener, or the photographic layer coating. It can be adjusted by changing the subsequent drying conditions and aging conditions. It is advantageous to use gelatin for the photographic layer, but other hydrophilic colloids can also be used. For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein, cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, cellulose sulfates, sugar derivatives such as sodium alginate and starch derivatives; polyvinyl alcohol. , Polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide,
Various synthetic hydrophilic polymer substances such as a single or copolymer such as polyvinyl imidazole and polyvinyl pyrazole can be used. As the gelatin, acid-treated gelatin may be used in addition to lime-treated gelatin, and gelatin hydrolyzate and gelatin enzyme-decomposed product may also be used. As the gelatin derivative, various compounds such as acid halides, acid anhydrides, isocyanates, bromoacetic acid, alkane sultones, vinyl sulfonamides, maleinimide compounds, polyalkylene oxides, epoxy compounds are added to gelatin. What is obtained by reaction is used.

As the above-mentioned gelatin / graft polymer, gelatin is a homopolymer or copolymer of vinylic monomers such as acrylic acid, methacrylic acid, derivatives thereof such as esters and amides, acrylonitrile and styrene. What grafted can be used. In particular, a graft polymer with a polymer having a certain degree of compatibility with gelatin, for example, a polymer such as acrylic acid, methacrylic acid, acrylamide, methacrylamide, or hydroxyacryl methacrylate is preferable.
Examples of these are U.S. Pat. Nos. 2,763,625 and 2,8.
31, 767, 2,956, 884 and the like. Typical synthetic hydrophilic polymer substances are, for example, West German patent application (OLS) 2,312,708, US Pat.
No. 620,751, No. 3,879,205, Japanese Patent Publication No. 4
No. 3-7561.

Examples of hardening agents include chromium salts (chromium alum, chromium acetate, etc.), aldehydes (formaldehyde, glyoxal, glital aldehyde, etc.), N-methylol compounds (dimethylol urea, methylol dimethylhydantoin, etc.), dioxane. Derivatives (2,3-dihydroxydioxane, etc.), active vinyl compounds (1,3,5-triacryloyl-hexahydro-s-triazine, bis (vinylsulfonyl) methyl ether, N, N'-methylenebis- [β- (vinyl Sulfonyl) propionamide] etc.), active halogen compounds (2,4-dichloro-6-hydroxy-s-triazine etc.), mucohalogen acids (mucochloric acid, mucophenoxycycloric acid etc.), isoxazoles, dialdehyde starch, 2-black And 6-hydroxy-triazinyl gelatin can be used alone or in combination. Particularly preferred hardeners are aldehydes,
They are active vinyl compounds and active halogen compounds. Further, the film swelling speed of the light-sensitive material in the present invention is 90% of the maximum swollen film thickness reached when processed in a color developing solution (38 ° C., 3 minutes 15 seconds), and the saturated swollen film thickness is defined as 1 / Two
When the time required to reach the film thickness is defined as the swelling rate T _1/2 , T _1/2 is preferably 20 seconds or less, and more preferably 10 seconds or less.

As the support used in the light-sensitive material according to the present invention, a white polyester support or a layer containing a white pigment for a display is provided on the support having a silver halide emulsion layer. A support may be used. Further, in order to improve the sharpness, it is preferable to apply an antihalation layer on the silver halide emulsion layer coated side or the back side of the support. In particular, the transmission density of the support is 0.3 so that the display can be viewed with both reflected and transmitted light.
It is preferably set in the range of 5 to 0.8.

The light-sensitive material according to the present invention may be exposed to visible light or infrared light. The exposure method may be low illuminance exposure or high illuminance short time exposure, and in the latter case, a laser scanning exposure method in which the exposure time per pixel is shorter than 10 ⁻⁴ seconds is preferable. Further, upon exposure, it is preferable to use the band stop filter described in US Pat. No. 4,880,726. As a result, light color mixture is removed, and color reproducibility is significantly improved.

[0121]

【Example】

Example 1 After a corona discharge treatment was applied to the surface of a paper support laminated on both sides with polyethylene, a gelatin subbing layer containing sodium dodecylbenzene sulfonate was provided, and various photographic constituent layers were further coated to form a layer structure shown below. A multilayer color printing paper (101) was prepared. The coating liquid was prepared as follows.

Preparation of coating solution for first layer Yellow coupler (ExY) 153.0 g, color image stabilizer (C
pd-1) 15.0 g, color image stabilizer (Cpd-2) 7.5 g,
16.0 g of color image stabilizer (Cpd-3) was used as a solvent (Solv-
1) 25 g, solvent (Solv-2) 25 g and ethyl acetate 1
This was dissolved in 80 cc, and this solution was emulsified and dispersed in 1000 g of a 10% gelatin aqueous solution containing 10 cc of 10% sodium dodecylbenzenesulfonate and 10 g of citric acid to prepare an emulsified dispersion A. On the other hand, silver chlorobromide emulsion A (cube, average grain size of 0.
A 3: 7 mixture of 88 μm large size emulsion A and 0.70 μm small size emulsion A (silver molar ratio). Coefficients of variation of grain size distribution are 0.08 and 0.10 respectively, and silver bromide for each size emulsion
0.3 mol% was locally contained on a part of the surface of the grain based on silver chloride) was prepared. In this emulsion, the blue-sensitive sensitizing dyes A and B shown below are large-sized emulsions A per mol of silver.
For, 2.0 × 10 ^-4 mol, respectively, also to the small size emulsion A, are respectively 2.5 × 10 ^-4 mol per mol. The chemical ripening of this emulsion was performed by adding a sulfur sensitizer and a gold sensitizer. The above emulsified dispersion A and this silver chlorobromide emulsion A were mixed and dissolved to prepare a coating solution for the first layer having the following composition. The emulsion coating amount indicates a coating amount equivalent to silver.

The coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer. As the gelatin hardening agent for each layer, 1-oxy-3,5-dichloro-s-triazine sodium salt was used. Also, Cpd-14 and C are added to each layer.
total amount pd-15 were added to each so that 25.0 mg / m ² and 50.0 mg / m ^2. The following spectral sensitizing dyes were used for the silver chlorobromide emulsion of each photosensitive emulsion layer. Blue-sensitive emulsion layer

[0124]

[Chemical 20]

(2.0 × 10 ^-4 mol for large size emulsion and 2.5 × 10 ^-4 mol for small size emulsion, respectively, per mol of silver halide) Green-sensitive emulsion layer

[0126]

[Chemical 21]

(Per mol of silver halide, 4.0 × 10 ⁻⁴ mol for large size emulsion, and for small size emulsion)
5.6 × 10 ^-4 mol) and,

[0128]

[Chemical formula 22]

(7.0 × 10 ⁻⁵ mol for large size emulsion and 1.0 × 10 ⁻⁴ mol for small size emulsion per mol of silver halide) Red-sensitive emulsion layer

[0130]

[Chemical formula 23]

(0.9 × 10 ^-4 mol for large size emulsion and 1.1 × 10 ^-4 mol for small size emulsion per mol of silver halide)

Further, the following compounds were added in an amount of 2.6 × 10 ^-3 mol per mol of silver halide.

[0133]

[Chemical formula 24]

For the blue-sensitive emulsion layer, the green-sensitive emulsion layer and the red-sensitive emulsion layer, 1- (5-methylureidophenyl)-
5-Mercaptotetrazole to silver halide 1
8.5 x 10 ^-5 mol, 7.7 x 10 ^-4 mol, 2.5 x 10 per mol
^-4 mol was added. Further, 4-hydroxy-6-methyl-1,3,3a, 7 was added to the blue-sensitive emulsion layer and the green-sensitive emulsion layer.
Tetrazaindene was added in an amount of 1 × 10 ^-4 mol and 2 × 10 ^-4 mol per mol of silver halide, respectively. Further, in order to prevent irradiation, the following dye (the amount in parentheses represents the coating amount) was added to the emulsion layer.

[0135]

[Chemical 25]

(Layer Structure) The composition of each layer is shown below. The numbers represent the coating amount (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 a white pigment (TiO ₂ : content 15% by weight) and a bluish dye (ultraviolet)]

First Layer (Blue Sensitive Emulsion Layer) Silver Chlorobromide Emulsion A 0.27 Gelatin 1.36 Yellow Coupler (ExY) 0.79 Color Image Stabilizer (Cpd-1) 0.08 Color Image Stabilizer (Cpd-2) 0.04 Color Image stabilizer (Cpd-3) 0.08 Solvent (Solv-1) 0.13 Solvent (Solv-2) 0.13

Second layer (color mixing preventing layer) Gelatin 1.00 Color mixing preventing agent (Cpd-4) 0.06 Solvent (Solv-2) 0.25 Solvent (Solv-3) 0.25 Solvent (Solv-7) 0.03

Third Layer (Green Sensitive Emulsion Layer) Silver chlorobromide emulsion (cubic, 1: 3 mixture of large size emulsion B having an average grain size of 0.55 μm and small size emulsion B of 0.39 μm (Ag mole ratio)) The coefficient of variation of the grain size distribution is 0.10 and 0.08, respectively, and AgBr is 0.8 mol% for each size emulsion.
0.13 gelatin 1.45 magenta coupler (ExM) 0.16 color image stabilizer (Cpd-2) 0.03 color image stabilizer (Cpd-5) 0.15 color Image Stabilizer (Cpd-6) 0.01 Color Image Stabilizer (Cpd-7) 0.01 Color Image Stabilizer (Cpd-8) 0.08 Solvent (Solv-3) 0.50 Solvent (Solv-4) 0.15 Solvent (Solv-5) 0.15

Fourth Layer (Color Mixing Prevention Layer) Gelatin 0.70 Color mixing inhibitor (Cpd-4) 0.04 Solvent (Solv-2) 0.18 Solvent (Solv-3) 0.18 Solvent (Solv-7) 0.02

Fifth layer (red-sensitive emulsion layer) Silver chlorobromide emulsion (cubic, 1: 4 mixture of large size emulsion C having an average grain size of 0.50 μm and small size emulsion C of 0.41 μm (Ag mole ratio)) . Coefficient of variation of particle size distribution is 0.09
And 0.11, AgBr 0.8 mol% was locally contained in a part of the surface of the grain based on silver chloride in each size emulsion) 0.20 Gelatin 0.85 Cyan coupler (ExC) 0.33 Ultraviolet absorber (UV-2) 0.18 Color image stabilizer (Cpd-1) 0.33 Color image stabilizer (Cpd-6) 0.01 Color image stabilizer (Cpd-8) 0.01 Color image stabilizer (Cpd-9) 0.01 Color image stabilizer (Cpd-10) 0.01 Color image stabilizer (Cpd-11) 0.01 Solvent (Solv-1) 0.01 Solvent (Solv-6) 0.22

Sixth layer (UV absorbing layer) Gelatin 0.55 UV absorbing agent (UV-1) 0.38 Color image stabilizer (Cpd-5) 0.02 Color image stabilizer (Cpd-12) 0.15

Seventh Layer (Protective Layer) Gelatin 1.13 Polyvinyl alcohol acrylic modified copolymer (modification degree 17%) 0.05 Liquid paraffin 0.02 Surfactant (Cpd-13) 0.01

[0145]

[Chemical formula 26]

[0146]

[Chemical 27]

[0147]

[Chemical 28]

[0148]

[Chemical 29]

[0149]

[Chemical 30]

[0150]

[Chemical 31]

After image-wise exposing the above light-sensitive material, a paper processor (aperture ratio of color development 0.005 cm ⁻¹ , carry-over amount of color developer by the light-sensitive material 30 ml / m ² , transport speed 1000 mm / min) was used. In the following processing steps, continuous processing (running test) was performed until the bleach-fixing tank capacity was replenished twice. A similar test was conducted by changing the aperture ratio of the paper processing machine with a floating pig as shown in Table 13. Further, as shown in Table 13, floats or floating fluids were added to the bleach-fix replenisher tank. Liquid paraffin was added to the color developing solution replenisher tank to cover the surface of the color developing solution replenisher to a thickness of 2 mm.

Treatment process Temperature Time Replenishment amount Tank capacity Color development 40.0 ° C 45 seconds 40 ml 5 liters Bleach fixing 35 ° C 45 seconds 30 ml 5 liters Rinse (1) 35 ° C 20 sec-2 liters Rinse (2) 35 ° C 20 sec − 2 liters Rinse (3) ^** 35 ℃ 20 seconds − 2 liters Rinse (4) ^** 35 ℃ 30 seconds 90 ml 3 liters Dry 80 ℃ 60 seconds * Replenishment amount per 1 m ^{2 of} light-sensitive material ** Fuji Photo Film Rinse RC-30 (3)
The rinse liquid is taken out from the rinse (3) and sent to the reverse osmosis membrane module (RC-30) by a pump. The permeated water obtained in the same tank was supplied to the rinse (4), and the concentrated water was returned to the rinse (3). The amount of permeated water to the reverse osmosis membrane module is 200-300 ml /
The pump pressure was adjusted so as to maintain min, and temperature control circulation was performed for 10 hours a day. (Rinse was a 4-tank countercurrent system from (4) to (1))

The composition of each processing liquid is as follows. [Color developer] [Tank solution] [Replenisher] Cation-exchanged water 800 ml 800 ml Triethanolamine 20.0 g 20.0 g Potassium hydroxide 5.0 g 15.0 g Ethylenediaminetetraacetic acid 3.0 g 3.0 g 4,5-Dihydroxybenzene-1 , 3-Sodium disulfonate 0.5g 0.5g Potassium chloride 15.8g-Potassium bromide 0.045g-Fluorescent brightener (SR-13) 5.0g 10.0g Sodium sulfite 0.1g 0.2g Disodium-N, N-bis (sulfona Ethyl) hydroxylamine 7.0 g 12.0 g N-ethyl-N (β-methanesulfonamidoethyl) -3-methyl-4-amino-4-aminoaniline / 3/2 sulfuric acid monohydrate 5.0 g 17.0 g potassium carbonate 26.3g 26.3g Add water 1000ml 1000ml pH (25 ℃ / with potassium hydroxide or sulfuric acid) 10.15 12.60

[Bleach-fixing solution] [Tank solution] [Replenishing solution] Water 600 ml 300 ml Ammonium thiosulfate (750 g / l) 90 ml 180 ml Ammonium sulfite 20 g 70 g Ethylenediaminetetraacetic acid ferric ammonium salt 0.11 mol 0.22 mol Ethylenediaminetetraacetic acid 0.01 mol 0.02 mol Compound (S-6) 0.10 mol 0.20 mol Imidazole 0.20 mol 0.40 mol Water added 1000 ml 1000 ml pH (at 25 ° C / nitric acid or ammonia water) 7.0 6.0

[Rinse] (common to tank solution and replenisher) Sodium chlorinated isocyanurate 0.02 g Deionized water (conductivity 5 us / cm or less) 1000 ml pH 6.5

After the running test was completed, the concentration of ammonium sulfite as a preservative in the bleach-fix solution was analyzed, and the liquid state of Rinse-3 solution (whether turbid or precipitated) was observed. The results are shown in Table 13. Indicated. Further, the coated sample was treated, and the whiteness, the amount of residual silver, and the coloring rate of the cyan dye were evaluated by the following methods, and the results are shown in Table 13. Whiteness: The unexposed coating sample was treated, and the minimum yellow density of the coated sample after the treatment was measured using a Macbeth densitometer. Residual silver amount: A sensitometer (FWH type, manufactured by Fuji Photo Film Co., Ltd., color temperature of light source: 3200 ° K) of the coated sample was used and subjected to gray step wedge exposure. (The exposure at this time was an exposure amount of 250 CMS with an exposure time of 0.1 seconds.) The coated sample after exposure was processed, and the amount of silver remaining at the maximum density point of the sample was measured by a fluorescent X-ray analysis method. Coloring rate of cyan dye: Sensitometer (FWH type, manufactured by Fuji Photo Film Co., Ltd., color temperature of light source 3200)
° K) was used to give a gray tone exposure for sensitometry. (The exposure at this time is an exposure amount of 0.1 Cs and an exposure amount of 250 CMS.) The coated sample after exposure is processed, the cyan maximum density of the sample is measured, and then the bleaching solution CN for color negative is used.
It was dipped in 16 × N2 bleach (Fuji Photo Film Co., Ltd.) for 2 minutes, washed with water and dried, and the cyan density was measured again. At this time, the rate of increase in the maximum cyan density (degree of leuco formation) was determined as the coloring rate P (%). P (%) = (cyan density after processing / cyan density after rebleaching) × 100 (%)

[0157]

[Table 13]

As is clear from Table 13, when the bleach-fix replenisher is coated with the floating fluid layer of the present invention and the opening ratio of the bleach-fix processing tank is 0.002 to 0.02 cm ^-1 , the bleach-fix solution is The concentration of ammonium sulfite in the solution was high, the liquid of rinse-3 was good, the yellow stain did not increase due to sulfurization, and the stability was good. The desilvering property was good and there was no leuco cyanation dye, and good results were obtained. . (Experiment Nos. 6 to 9) When the conventional floating ball was used without using the floating fluid of the present invention, the stability was poor, the rinse-3 was sulphated, the yellow stain was increased, and the bleach-fix solution was low. It turns out that replenishment is difficult. (Experiment Nos. 1 to 3) Even when the floating fluid of the present invention is used, when the opening ratio of the bleach-fix processing tank is smaller than 0.002 cm ^-1 ,
There is a problem that desilvering and leuco cyanation occur, and when it is more than 0.02 cm ^-1 , stability is poor and yellow stain rises, making it difficult to reduce the replenishment of the bleach-fixing solution. I know there is. (Experiment No.
4, 5, 10, 11) From the above, the specific effect of the combination of the coating of the replenisher with the floating fluid of the present invention and the specific opening ratio of the processing tank is clear. Further, in the present invention, more preferable results were obtained when the floating fluid was liquid paraffin.

Example 2 Fuji Color Paper FAV (Lot
942-406, Glossy area) and Fuji Photo Lab Fuji Mini Lab Paper Printer Processor PP12
A running test was performed in the same manner as in Example 1 using 50V. The processing steps and processing liquid formulations are shown below. Treatment process Temperature Time Replenishment amount ^* Color development 40 ℃ 45 seconds 40 ml Bleach-fix 38 ℃ 45 seconds 30 ml Rinse (1) 38 ℃ 20 s − Rinse (2) 38 ℃ 20 s − Rinse (3) ^** 38 ℃ 20 seconds-rinse (4) ^** 38 ° C 30 seconds 90 ml * Replenishment amount per 1 m ^{2 of} light-sensitive material ** Rinse (3) RC-30 manufactured by Fuji Photo Film Co., Ltd.
The rinse liquid is taken out from the rinse (3) and sent to the reverse osmosis membrane module (RC-30) by a pump. The permeated water obtained in the same tank was supplied to the rinse (4), and the concentrated water was returned to the rinse (3). The pump pressure was adjusted so that the amount of permeated water to the reverse osmosis membrane module was maintained at 200 to 300 ml / min, and the temperature was controlled and circulated for 10 hours a day. (Rinse was a 4-tank countercurrent system from (4) to (1))

[Color developer] Same as in Example 1 [Bleaching fixer] [Tank solution] [Replenisher] Water 600 ml 300 ml Ammonium thiosulfate (750 g / liter) 95 ml 200 ml Ammonium sulfite 15 g 75 g Ethylenediamine tetra Ferric acetate ammonium salt 0.10 mol See Table 14 Ethylenediaminetetraacetic acid 0.01 mol 0.02 mol Compound (S-6) 0.07 mol 0.15 mol Imidazole 0.3 mol 0.65 mol Water added 1000 ml 1000 ml pH (25 ° C / nitric acid or aqueous ammonia) 6.85 6.20

[Rinse] (common to tank liquid and replenisher) Sodium chlorinated isocyanurate 0.02 g Water 1000 ml pH 6.5

After image-wise exposing the above light-sensitive material, continuous processing (running test) was carried out by using the above-mentioned printer processor until the capacity of the bleach-fixing tank was doubled in the above processing step. Further, the same test was carried out by changing the ethylenediaminetetraacetic acid ammonium ferric ammonium salt concentration of the bleach-fix replenisher and the presence or absence of the floating fluid as shown in Table 14. Liquid paraffin was added to the color developing solution replenisher tank to cover the surface of the color developing solution replenisher to a thickness of 2 mm.

After the running test, the concentration of ammonium sulfite as a preservative in the bleach-fix solution was analyzed in the same manner as in Example 1, and the ratio of the ferrous complex salt concentration to the total iron complex salt concentration in the bleach-fix solution was analyzed. F ²⁺ / Fe (%), Fe ²⁺ / Fe (%) = (ferrous iron complex salt concentration / total iron complex salt concentration) × 100 (%) were analyzed by a coloring method using bathophenanthroline, and the results were obtained. Is shown in Table 14. The light-sensitive material was processed and the whiteness, the amount of residual silver, and the coloring rate of the cyan dye were measured in the same manner as in Example 1, and the results are shown in Table 14.

[0164]

[Table 14]

As is clear from Table 14, when the bleach-fixing replenisher is coated with the floating fluid layer of the present invention and the opening ratio of the bleach-fixing processing tank is within the range of the present invention, a preservative in the bleach-fixing solution is used. The concentration of sulfite was high, there was no increase in yellow stain due to sulfurization, and the result was excellent in stability. The results also show good desilvering properties and cyan color development. In the present invention, the concentration of the iron complex salt in the bleach-fixing replenisher is 0.15 to 0.15.
When the amount was 0.35 mol / liter, the stability was excellent, and the desilvering property and the cyan color development were particularly good.
In the present invention, the concentration of the iron complex salt in the bleach-fixing replenisher is 0.
When it is 15 mol / liter or less, stability is excellent, but
The ratio of the ferrous salt increases, and the desilvering property and the cyan color development ratio tend to decrease. When the concentration of the iron complex salt is 0.35 mol / liter or more, the desilvering property and the cyan color development are excellent,
The sulfurous acid concentration tends to decrease and the yellow minimum density tends to increase.

Example 3 The coating sample prepared in Example 1 and Fuji Mini Lab Paper Printer Processor PP12 manufactured by Fuji Photo Film Co., Ltd.
A running test was conducted in the same manner as in Example 2 using 50V. Processing process Temperature Time Replenishment amount ^* Color development 40 ℃ 45 seconds 40 ml Bleach fixing 40 ℃ 45 seconds 30 ml Rinse (1) 40 ℃ 20 seconds − Rinse (2) 40 ℃ 20 seconds − Rinse (3) 40 ℃ 20 seconds -Rinse (4) 40 ° C 20 seconds 150 ml * Replenishing amount per 1 m ^{2 of} light-sensitive material material [color developer] Same as in Example 1

[Bleach-fixing solution] Part A Water 300 ml Ethylenediaminetetraacetic acid Ammonium ferric acid 0.25 mol Compound (S-7) 0.15 mol Water is added to 500 ml pH (at 25 ° C./ammonium nitrate water) 6.0 Part B Water 150 ml Ammonium thiosulfate (75 g / liter) 190 ml Ammonium sulfite 75 g Imidazole 0.2 mol Water added 500 ml pH (25 ° C / ammonium nitrate water) 6.0 [Replenisher] Part A 500 ml + Part B 500 ml [Tank Liquid] 500 ml of water + 500 ml of replenisher

[Rinse] (common to tank solution and replenisher) Sodium chlorinated isocyanurate 0.2 g Deionized water (conductivity 5 us / cm or less) 1000 ml pH 6.5

The above color developing tank solution, color developing replenishing solution, and bleach-fixing parts A and B solutions were placed in the flexible processing solution container having the bellows part described in the text, and each solution was prepared as follows. did. Color development tank liquid 2500ml container D Color development replenisher 2500ml container D Bleach-fixing replenisher Part A Volume 2000ml container C Bleach-fixing replenisher Part B Volume 2000ml container C Where bleach-fixing replenishment The solution was prepared by adding Part A into the replenishment tank, then adding Part B, without stirring.
It was uniformly mixed without stirring.

After the image-wise exposure of the coated sample, continuous processing was carried out by using the printer processor until replenishing the capacity of the bleach-fixing tank by twice in the processing step. Also, by modifying the above printer processor, the circulating amount of the bleach-fixing tank liquid was changed as shown in Table 15, and the presence or absence of the liquid floating on the replenishing liquid surface was changed as shown in Table 15, and the same test was conducted. I went. Liquid paraffin was added to the color developing solution replenisher tank to cover the surface of the color developing solution replenisher to a thickness of 2 mm.

After the running test, the ratio of the ferrous complex salt concentration to the concentration of ammonium sulfite as a preservative and the concentration of total iron in the bleach-fixing solution was Fe ²⁺ / as in Example 2.
Fe (%) was measured by the same method as in Example 2, and the results are shown in Table 15. Further, the coated sample was treated, and the whiteness, the amount of residual silver, and the coloring rate of the cyan dye were measured in the same manner as in Example 1, and the results are shown in Table 15.

[0172]

[Table 15]

As is clear from Table 15, when the bleach-fixing replenisher is coated with the floating fluid layer of the present invention and the opening ratio of the bleach-fixing processing tank is within the range of the present invention, the composition of the bleach-fixing solution is kept constant. The concentration of sulfite as an agent was high, there was no increase in yellow stain due to sulfurization, and the results were excellent in stability, and the results were good desilvering and cyan color development. Among the present invention, when the circulating amount of the processing liquid in the bleach-fixing processing tank is 30 to 150% of the total amount of the processing liquid per minute, the stability is excellent and the desilvering property and the cyan color development rate are excellent. Particularly good results were shown. In the present invention, when the circulating amount of the processing liquid in the bleach-fixing processing tank is less than 30% of the total amount of the processing liquid per minute, the stability is excellent, but the ratio of the ferrous salt increases. , The desilvering property and the cyan color development rate tend to decrease. When the circulation amount is more than 150%, the desilvering property and the cyan color development are excellent, but the sulfite concentration tends to decrease and the yellow minimum concentration tends to increase.

Example 4 In the same manner as in Experiment No. 4 of Example 2, except that the bleaching agent ethylenediaminetetraacetic acid ferric ammonium salt in the bleach-fixing solution and the bleach-fixing replenishing solution was replaced with the compound E-in the text. 1
Ferric ammonium salt ([S, S] form) was replaced with ethylenediaminetetraacetic acid at the same concentration, and the compound E-
When a running test was carried out by replacing 1 with the same concentration, good results were obtained.

Example 5 In the same manner as in the color reversal paper and its treatment described in Example 1 of JP-A-4-298742, the liquid paraffin of the present invention was added to the bleach-fix replenisher as a replenisher. When the running ratio was adjusted by adjusting the opening ratio of the bleach-fixing treatment tank to 0.02 cm ^-1 , the stability, desilvering property, and recoloring property (cyan dye leuco-formation) were added. Good results excellent in prevention) were obtained.

Example 6 In the same manner as in the color negative film and its treatment described in Example 2 of JP-A-3-200145, except that the liquid paraffin of the present invention was replenished with the bleach-fixing solution to a liquid level of 5
The amount of coating in mm was added, and the opening ratio of the bleach-fixing treatment tank was adjusted to 0.02 cm ^-1 and a running test was carried out. Good results excellent in prevention) were obtained.

[0177]

INDUSTRIAL APPLICABILITY According to the present invention, the stability of the bleach-fixing solution is remarkably improved, it has good desilvering property and cyan color forming property (prevention of leuco formation), and the replenishment of the bleach-fixing solution is extremely low and the waste liquid is reduced. Has become feasible.

[Brief description of drawings]

FIG. 1 is a front view of a substantially rectangular container for a flexible processing liquid having a bellows portion.

FIG. 2 is a front view of a substantially round container for a flexible processing liquid having a bellows portion.

[Explanation of symbols]

 1: Cap 2: Inner plug 3: Mouth part 4: Bellows part

Claims (4)

[Claims] 1. A method of processing a silver halide color photographic light-sensitive material with a bleach-fixing solution after a color developing solution, in which the liquid surface of the bleach-fixing replenisher in a bleach-fixing replenisher tank is covered with a fluid layer of a floating fluid. , Opening ratio of bleach-fix processing tank (Area in which the liquid contacts the air (cm ² ) with respect to the total processing liquid (cm ³ ))
Ratio) is 0.002 to 0.02 cm ⁻¹ , the method for processing a silver halide color photographic light-sensitive material. 2. The floating fluid is liquid paraffin or liquid saturated hydrocarbon.
The processing method described. 3. The processing method according to claim 1, wherein the bleach-fixing replenisher contains 0.15 to 0.35 mol / liter of an organic acid iron complex salt. 4. The processing method according to claim 1, wherein the circulating amount of the bleach-fixing solution in the bleach-fixing processing tank is 30 to 150% of the total amount of the processing solution per minute.