JPH0711697B2 - Method and apparatus for processing color photographic light-sensitive material - Google Patents

Description

The present invention relates to a method for processing two silver halide color photographic light-sensitive materials (hereinafter abbreviated as light-sensitive materials) of different types, and an apparatus for processing these two light-sensitive materials. Regarding

(Prior Art) A silver halide color photographic light-sensitive material is developed in a color photographic developing station. Generally, a negative color light-sensitive material for photography is developed to form a negative image, the negative image is printed on a color positive light-sensitive material for printing by using a printing machine, and the light-sensitive material is processed by a developing device different from the developing device. To obtain a positive image on the photosensitive material. As described above, in the process of obtaining a color photographic image, it is necessary to install an automatic developing machine for a negative photosensitive material, an automatic developing machine for a positive photosensitive material, and an automatic photographic printing apparatus for three steps. Usually, a predetermined space is required as a work space around these devices.

In particular, a space for installing a tank for replenisher, etc. according to the tank liquid exchange and the amount of processing, a space for dissolving and adjusting the replenisher, a dissolved replenisher around the automatic processor among these devices. The installation area required for replenishment work, such as the space for transferring the replenishment tank to the replenishment tank and the space required for adjusting the replenishment cock, occupies a considerable proportion in the photo lab. Further, the development processing step of the light-sensitive material is composed of two or more processing steps as described above, and a replenisher is prepared for each replenishment, so that a large space is required as described above. These replenishment operations require a great deal of time because the dissolution adjustment of the replenisher is frequent.

Further, as a recent trend, there is a shift from large-scale laboratories to small-scale laboratories for automatic color development processing, and so-called minilabs with a small processing amount are rapidly emerging. In such a small size developing station, the size and space saving of the automatic developing machine can be reduced, the work can be simplified and shortened, and it can be installed in any place where there is no water supply or drainage facility, and the piping can be installed. There is a strong demand for the appearance of an automatic processor that is unnecessary and can save energy costs and washing water. As a technique for responding to such a demand, the present inventors have found that Japanese Patent Application Nos. 59-69158, 59-69161 and 59
-81692 and Japanese Patent Application No. 59-58351 propose a replenisher tank capable of preparing a processing solution that does not require a dissolution tank necessary for preparing the processing solution, and Japanese Patent Application No. 59-69159. In Japanese Patent Application No. 59-69160 and the like, a simple method for preparing a treating solution and a treating agent kit using the above replenisher tank were proposed.

Furthermore, the inventors of the present invention have disclosed in Japanese Patent Application No. 59-89288 and Japanese Patent Application No. 59-1
No. 08288, Japanese Patent Application No. 59-109607, etc., proposed an automatic processor having substantially no washing tank.

[Problems trying to solve the invention]

The present invention has been made to further develop the above-mentioned processing technique, and is a method for processing a color photographic light-sensitive material that saves the installation area of an automatic developing machine and easily secures a work space around the automatic developing machine. The first purpose is to provide. A second object is to provide a method for processing a color photographic light-sensitive material, which simplifies the process of dissolving the processing solution and reduces the frequency and time of dissolution. A third object of the present invention is to provide a color photographic light-sensitive material processing apparatus which does not substantially use rinsing water, has low energy cost and pollution load, and is easy to carry.

[Means for solving problems]

The present invention has been carried out in order to achieve the above-mentioned object, and as a result, a processing method in which a processing solution for replenishing a processing tank for developing a silver halide color photographic light-sensitive material is replenished with a processing solution according to the processing amount is used. In, at least two color developing tanks for two different types of silver halide color photographic light-sensitive materials are provided, one of which is supplemented with a replenisher according to the processing amount of the color photographic light-sensitive material and the other of which is Is a method for processing a color photographic light-sensitive material, characterized in that the solution in the color developing tank is replenished, and a color developing tank, a tank having a bleaching function,
It is equipped with a fixing system and a stabilizing bath, and a processing system (a) that does not have a washing bath for washing the photosensitive material to be processed with running water, a color developing bath, a bath having a bleaching function and a stabilizing bath. A processing system (b) having no water-washing tank for cleaning the light-sensitive material to be processed is provided in parallel and close to the color development tank of the processing system (b), and the color development replenisher is replenished to the color development tank. Color photographic light-sensitive material having a connecting means for the overflow of the color developing tank to the color developing tank of the processing system (a) and not providing a means for directly replenishing the color developing replenisher to the color developing tank of the processing system (a). It has been found that the above-mentioned object of the present invention is achieved by a material processing apparatus.

In the present invention, "two different types of silver halide color photographic light-sensitive materials" mean, for example, a color negative light-sensitive material for photographing (color negative film), a color positive light-sensitive material for printing (color paper), a color reversal film and a color. It means a combination of different kinds of silver halide photographic light-sensitive materials such as reversal paper, color negative film and color X-ray film. In particular, a color negative film and a color paper, and a color reversal film and a color reversal paper are two different types of silver halide photographic light-sensitive materials of the present invention.

That is, according to the present invention, two different types of silver halide color photographic light-sensitive materials can be processed by replenishing a common replenishing solution, so that a space for installing a replenishing tank and a replenishing work are required. Not only does it save space, but it also reduces dissolution frequency and dissolution time. In particular, small-sized developing laboratories do not have the space to store a large amount of various types of replenisher solutions prepared by dissolution, and a small amount of replenisher solution can be prepared at a time by a small-sized processing agent kit. The effect of the present invention is particularly high.

The present invention is preferably applied to a combination of a color negative film and a color paper as described above. That is, usually, one print is produced from one shot of the color negative film, and even if some additional printing is taken into consideration, the processing area of the color negative film and the processing area of the color paper are substantially proportional. Therefore, if either one of them, for example, the automatic developing machine is designed so that the replenisher is replenished according to the processing amount of the color negative film and the replenisher prescription is designed, both of them can be replenished at a specific time of day. Even though the throughputs are different, the averages of one day show that the throughputs of both are well balanced.
It is possible to avoid the fluctuation of the composition of the processing liquid which is caused by the imbalance of the processing amounts of the two light-sensitive materials of extremely different types.

Further, since the other photosensitive material is processed by the overflow liquid of the processing tank for processing one photosensitive material without processing the same photosensitive material of two different photosensitive materials, for example, one photosensitive material to the other photosensitive material is processed. When a compound that adversely affects the processing of is eluted, by treating the other photosensitive material with the overflow solution obtained by processing the photosensitive material that does not elute with such a harmful compound, the case of processing in substantially the same layer You can get the same effect.

In the present invention, the automatic development for processing two different types of silver halide color photographic light-sensitive materials is a replenisher for a processing device that completely separates two to process one color photographic light-sensitive material. The overflow of the processing tank to be replenished may flow into the processing tank of the other processing apparatus for processing the color photographic light-sensitive material. Replenishing devices such as tanks, drain cocks, filters, etc. may all be arranged on one side of each processing device, and the parts where these devices are not arranged may be arranged back to back. May be configured as one completely integrated processing device.

In the processing method of the present invention, the processing bath may have any processing bath in addition to the color developing bath. Representative examples of preferred treatment methods include the following steps.

(1) Color development → bleach-fixing → washing with water (2) Color developing → bleach-fixing → washing with a small amount of water → water washing (3) Color developing → bleach-fixing → washing → stable (4) Color developing → bleach-fixing → stable (5) Color developing ->Bleach-fixing-> 1st stability-> 2nd stability (6) Color development-> Water washing-> Bleach fixing-> Water washing (7) Color development->Stable-> Bleach fixing-> Stable (8) Color development->Stop-> Bleach fixing-> Water washing (9) Color development → Stop → Bleach fixing → Stable (10) Color development → Bleach → Wash → Fix → Wash → Stable (11) Color development → Bleach → Fix → Wash → Stable (12) Color development → Bleach → Fix → 1st stability → 2nd stability (13) Color development → bleaching → small amount of water washing → fixing → small amount of water washing → water washing → stable (14) color development → pre-fixing → bleach-fixing → 1st stability → 2nd stability (15) color development → bleaching acceleration → Bleach → Fixing → 1st stability → 2nd stability (16) Color development → Rinse with small amount of water → Bleach → Rinse with small amount of water → Wear → small amount water washing → water washing → stabilizing (17) Color development → stopping → bleaching → small amount water washing → fixing → small amount water washing → water washing → stabilizing (18) black and white development → water washing (or stabilizing) → reversal → color developing →
Bleaching → Fixing → Washing (or omission) → Stable (19) Pre-hardening → Neutralization → Black and white development → Stop → Color development → Bleaching → Fixing → Washing (or omission) → Stable Among these processing steps, Since the effect is more prominent, (4), (5), (7), (9), (1
The treatment steps of 2), (14) and (15) which do not have the washing treatment are more preferably used in the present invention.

Two different types of color photographic light-sensitive materials are processed in any one of the above-mentioned processes, and the processing steps of these two color photographic light-sensitive materials may be the same or different. May be.

In the present invention, of the two processing steps selected from the above processing steps, only one of the two color developing tanks used for color development is replenished and the overflow is led to the other.
There is no particular limitation on the structure of the other processing tanks for one processing step, and any structure can be adopted.

The following configurations can be given as specific examples of the configuration of the processing tank of the processing apparatus of the present invention.

However, in the specific examples of (a) to (f) above, the replenishment of the replenisher is Indicates the direction of the overflow liquid, and → indicates the traveling direction of the photographic light-sensitive material.

The present invention is particularly preferably applied to a processing apparatus having no water washing tank for washing a silver halide color photographic light-sensitive material with running water having a communication pipe with the outside. In such a treatment device, since there is no water pipe for flushing water, the work is easy and the effect of the present invention can be maximized, and a large amount of water is not used, and the cost is saved.

Aromatic primary amine color developing agents are used in the color developing solution used in the present invention, and these include those widely used in various color photographic processes. These color developing agents include aminophenol-based and p-phenylenediamine-based derivatives.
Since these compounds are more stable than the free state, they are generally used in the form of salts, for example, hydrochlorides or sulfates. Further, these compounds are generally preferably used in a concentration of about 0.1 g to 30 g for the color developer 1, and more preferably used in a concentration of about 1 g to about 15 g for 1.

A particularly useful p-phenylenediamine color developing agent is an aromatic primary amine color developing agent having at least one water-soluble amino group, and particularly preferably a compound represented by the following general formula [A]. is there.

General formula [A] In the formula, R ₁₇ represents a hydrogen atom, a halogen atom or an alkyl group, and the alkyl group has a linear or branched carbon number of 1 to 5
Represents an alkyl group and may have a substituent. R
₁₈ and R ₁₉ represent a hydrogen atom, an alkyl group or an aryl group, and these groups may have a substituent, and in the case of an alkyl group, an alkyl group substituted with an aryl group is preferable. And at least one of R ₁₈ and R ₁₉ is an alkyl group substituted with a water-soluble group such as a hydroxyl group, a carboxylic acid group, a sulfonic acid group, an amino group or a sulfonamide group, or CH _{2 q
Or} R ₂₀ . This alkyl group may further have a substituent.

R ₂₀ represents a hydrogen atom or an alkyl group, which represents a linear or branched alkyl group having 1 to 5 carbon atoms, and q and r each represent an integer of 1 to 5.

Next, typical examples of the compound represented by the general formula [A] will be shown, but the invention is not limited thereto.

Exemplified compound The color developing solution may contain a known developing component in addition to the aromatic primary amine color developing agent. For example, as a preservative, a water-soluble salt of hydroxylamine,
For example, sulfates, hydrochlorides and phosphates. As the alkaline agent, buffering agent, etc., sodium hydroxide, silicate, sodium carbonate, potassium metaborate, boric acid, etc. are added alone or in combination. Further, disodium hydrogen phosphate, sodium bicarbonate, boric acid or the like can be used for the necessity of preparation or for the purpose of increasing ionic strength.

If necessary, it is also possible to add an inorganic or organic antifoggant, and typical examples of these compounds include inorganic halide compounds such as potassium bromide and potassium iodide, and U.S. Pat. 6-nitrobenzimidazoles described in No. 2,497,917 and No. 2,656,2
5-nitrobenzimidazole described in No. 71, in addition to this,
Including o-phenylenediamine, mercaptobenzimidazole, mercaptobenzoxazole, thiouracil, 5-methylbenzotriazole, or Japanese Patent Publication
Examples thereof include the heterocyclic compounds described in Japanese Patent Publication No. 46-41675.

In addition to these various components, Japanese Examined Patent Publication Nos. 46-19039 and 45-6
A development inhibitor disclosed in each of Japanese Patent Publication No. 149 and U.S. Pat. No. 3,295,976 and a development accelerator may be added if necessary.
Some of these development accelerators are US Pat.
No. 3,671,247, various pyridinium compounds represented by JP-B-44-9503, other cationic compounds, cationic dyes such as phenosafranine,
Neutral salts such as thallium sulfate, U.S. Pat.No. 2,533,990,
No. 2,531,832, No. 2,950,970, No. 2,577,127
And nonionic compounds such as polyethylene glycol and its derivatives and polythioethers described in JP-B-44-9504, organic solvents and organic amines described in JP-B-44-9509, ethanolamine, ethylenediamine, diethanolamine, and triethanolamine. Includes ethanolamine and the like.
Also, benzyl alcohol, phenethyl alcohol, and the others described in US Pat. No. 2,304,925, and
Acetylene glycol, methyl ethyl ketone, cyclohexanone, thioethers, pyridine, ammonia, hydrazine and amines are also effective development accelerators. If necessary, ethylene glycol, methyl cellosolve, methanol, acetone, dimethylformamide, β
-Cyclodextrin, other Japanese Patent Publication Nos. 47-33378 and 4
The compounds described in JP-A-4-9509 can be used as an organic solvent for increasing the solubility of the developing agent.

The color developing solution may also contain various chelating agents as a water softening agent and a heavy metal sequestering agent. Examples of such chelating agents include phosphates such as polyphosphates, nitrilotriacetic acid, 1,3-diaminopropanoltetraacetic acid, diethylenetriaminepentaacetic acid, aminopolycarboxylic acids such as hydroxyethyliminodiacetic acid, citric acid, and glycolic acid. Oxycarboxylic acid, 1-hydroxyethylidene-1,
Organic phosphonic acids such as 1-diphosphonic acid, aminopolyphosphonic acids such as aminotri (methylenephosphonic acid), 1,2-
Examples include polyhydroxy compounds such as dihydroxybenzene-3,5-disulfonic acid.

Further, an auxiliary developing agent can be used together with the developing agent. Examples of these auxiliary developers include N-methyl-p-aminophenol hexalphate (methol), phenidone, N, N'-diethyl-p-aminophenol hydrochloride, N, N, N ', N'-tetrahydrochloride. Methyl-p-phenylenediamine hydrochloride and the like are known, and the addition amount thereof is usually preferably 0.01 g to 1.0 g / l. Besides this,
If necessary, a competitive coupler, a fogging agent, a colored coupler, a development inhibitor releasing type coupler (so-called DIR coupler), a development inhibitor releasing compound or the like can be added.

The color developing solution can be used at a pH of 8 to 14, more preferably pH.
Used from 9.5 to pH12. The treatment temperature is 80 ° C. or lower, preferably 55 ° C. or lower, most preferably 45 ° C. or lower to suppress evaporation. The treatment time is preferably 10 minutes or less, more preferably 5 minutes or less.

In the present invention, a bleaching or bleach-fixing solution is used in addition to the color developing solution. These bleaching or bleaching-fixing solutions contain an organic acid ferric iron complex salt such as ethylenediaminetetraacetic acid ferric iron complex salt as a bleaching agent. Used.

Particularly preferable examples include ferric iron complex salts of organic acids shown below.

(1) diethylenetriaminepentaacetic acid (2) diethylenetriaminepentamethylenephosphonic acid (3) cyclohexanediaminetetraacetic acid (4) ethylenediaminetetraacetic acid (5) methyliminodiacetic acid (6) propyliminodiacetic acid (7) butyliminodiacetic acid (8) cyclohexane Diaminetetramethylenephosphonic acid (9) Triethylenetetramine hexaacetic acid (10) Triethylenetetramine hexamethylenephosphonic acid (11) Glycol ether diamine tetraacetic acid (12) Glycol ether diamine tetramethylenephosphonic acid (13) 1,2-Diaminopropane Tetraacetic acid (14) 1,2-Diaminopropane tetramethylenephosphonic acid (15) 1,3-Diaminopropan-2-ol tetraacetic acid (16) 1,3-Diaminopropan-2-ol tetramethylenephosphonic acid (17) Ethylenediaminedioltohydroxypheny Acetic acid (18) Ethylene diamine diorthohydroxy phenyl methylene phosphonic acid (19) Ethylene diamine tetramethylene phosphonic acid The ferric iron complex salt of an organic acid can be used by arbitrarily selecting one of these, and if necessary, selecting two. The above may be used in combination.

The ferric iron complex salt of the organic acid is a free acid (hydrogen salt), an alkali metal salt such as a sodium salt, a potassium salt, a lithium salt, or an ammonium salt, or a water-soluble amine salt,
For example, it is used as a triethanolamino salt, but preferably potassium salt, sodium salt and ammonium salt are used. At least one of these ferric complex salts may be used, but two or more thereof may be used in combination. The amount used can be arbitrarily selected and needs to be selected depending on the amount of silver of the light-sensitive material to be processed and the silver halide composition. For example, it can be used in an amount of 0.01 mol or more per 1 solution used,
It is preferably used in an amount of 0.05 to 0.6 mol. It should be noted that it is desirable that the replenisher be used after being concentrated to the maximum solubility so that the replenisher can be concentrated and low in replenishment.

A peroxide may also be used as the bleaching agent, and as the peroxide, hydrogen peroxide, percarbonate, perborate and persulfate are preferably used. In addition, examples of these salts include potassium salts, sodium salts, ammonium salts and the like, and the preferable amount thereof is in the range of 0.01 to 6.0 mol / l, more preferably 0.05 to 3.0 mol / l.

The bleaching solution and the bleach-fixing solution can be used at a pH of 0.2 to 9.5, preferably 1 to 9, and more preferably 2.0 to 8.5.
The processing temperature is 80 ℃ or below, preferably 55 ℃
Hereafter, it is most preferably used at 45 ° C. or lower while suppressing evaporation and the like. The treatment time is preferably within 8 minutes, more preferably 6 minutes.
Within minutes.

The bleaching solution or the bleach-fixing solution may contain various additives together with the bleaching agent as described above. As the additive, it is particularly preferable to contain an alkali halide or an ammonium halide such as potassium bromide, sodium bromide, sodium chloride, ammonium bromide, potassium iodide, sodium iodide, ammonium iodide. In addition, acid buffers, acetates, carbonates, pH buffers such as phosphates, solubilizers such as triethanolamino, acetylacetone, phosphonocarboxylic acids, polyphosphoric acids, organic phosphonic acids, oxylcarboxylic acids, polycarboxylic acids, Alkylamines, polyethylene oxides and the like which are known to be added to ordinary bleaching solutions can be appropriately added.

The bleach-fix solution contains a composition containing a small amount of a halogen compound such as potassium bromide, or conversely, a bleach-fix solution containing a composition containing a large amount of a halogen compound such as potassium bromide or ammonium bromide. Further, a special bleach-fixing solution having a composition comprising a combination of the bleaching agent of the present invention and a large amount of a halogen compound such as potassium bromide can be used.

As the halogen compound, other than potassium bromide, hydrochloric acid, hydrobromic acid, lithium bromide, sodium bromide,
Ammonium bromide, potassium iodide, sodium iodide, ammonium iodide and the like can also be used.

The silver halide fixing agent contained in the above bleach-fixing solution is a compound which reacts with silver halide to form a water-soluble complex salt, such as potassium thiosulfate, sodium thiosulfate, thio Thiosulfate such as ammonium sulfate, potassium thiocyanate, sodium thiocyanate, thiocyanate such as ammonium thiocyanate, thiourea, thioether, high concentration bromide,
A typical example is iodide. These fixing agents are preferably used in an amount of 5 g / l or more, more preferably 50 g / l or more, and even more preferably 70 g / l or more.

This bleach-fix solution contains boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, ammonium hydroxide as in the case of the bleaching solution. A pH buffer agent composed of various salts such as the above can be contained alone or in combination of two or more kinds. Further, various fluorescent whitening agents, antifoaming agents or antifungal agents may be contained. Also hydroxylamine, hydrazine,
Preservatives such as sulfites, isomeric bisulfites, bisulfite adducts of aldehydes and ketone compounds, acetylacetone, phosphonocarboxylic acids, polyphosphoric acids, organic phosphonic acids, oxycarboxylic acids, polycarboxylic acids, dicarboxylic acids and aminopoly Organic chelating agents such as carboxylic acids, stabilizers such as nitroalcohol and nitrates, solubilizers such as alkanolamines, stain inhibitors such as organic amines, other additives, organic solvents such as methanol, dimethylformamide and dimethylsulfoxide. Can be appropriately contained.

The stabilizer used in the present invention neutralizes, desalts, and inactivates the pre-bath components (for example, the bleach-fixing solution component or the fixing solution component) brought in by adhering to the light-sensitive material from the pre-bath. A function that does not deteriorate the storage stability of the dye, a draining bath function that prevents contamination such as uneven washing with water, a function that blocks the active points of unreacted couplers to stabilize the color image, a color adjustment function that colors the color image, and charging Some have a function such as an antistatic function by containing an inhibitor, and these functions may be combined.

When the stabilizing solution contains at least one compound selected from the following group, the generation of silver sulfide in the stabilizing solution is improved with respect to the low renewal rate processing, and the unexposed portion of the processed light-sensitive material is treated. Stain also has the effect of being improved, and is therefore particularly preferably used.

[Compound] (A) Benzoic acid type compound (B) Phenol type compound (C) Thiazoline type compound (D) Imidazole type compound (E) Guanidine type compound (F) Carbamate type compound (G) Morpholine type compound (H) Four Phosphonium compounds (I) quaternary ammonium compounds (J) urea compounds (K) isoxazole compounds (L) propanolamine compounds (M) amino acid compounds (N) triazine compounds (O) pyridine compounds Stable Specific examples of the compounds (A) to (O) contained in the liquid include, but are not limited to, the following compounds.

[Exemplified compound]

(1): sodium orthophenylphenol (2): 2-octyl-4-isothiazoline (3): benzisothiazolin-3-one (4): 2-methyl-4-isothiazolin-3-one (5): 5- Chloro-2-methyl-4-isothiazoline-
3-one (6): 2-thiomethyl-4-ethylamino-6- (1,2
-Dimethylpropylamino) -s-triazine (7): Hexahydro-1,3,5-tris (2-hydroxyethyl) -s-triazine (8): 4- (2-nitrobutyl) morpholine (9): 4- (3-Nitrobutyl) morpholine (10): 2- (4-thiazoline) benzimidazole (11): Dodecylguanidine hydrochloride (12): Hydroxybenzoic acid methyl ester (13): Hydroxybenzoic acid propyl ester (14): Hydroxy Benzoic acid n-butyl ester (15): p-hydroxybenzoic acid (16): Benzoic acid methyl ester (17): Orthocyclohexylphenol (18): 1,2-Benzisothiazolin-3-one (19): 2- Octyl-4-isothiazolin-3-one (20): 2- (4-thiazoline) -benzimidazole (21): 2,6-dimethylpyridine (22): 2,4,6 -Trimethylpyridine (23): Sodium-2-pyridinethiol-1-oxide (24): Cyclohexidine (25): Polyhexamethylene biguanidine hydrochloride (26): Methyl-1- (butylcarbamoyl) -2- Benzimidazole carbamate (27): Methylimidazole carbamate (28): Tri-n-butyl-tetradecylphosphonium chloride (29): Triphenyl-nitrophenylphosphonium chloride (30): Dodecyldimethylbenzylammonium chloride (31): Didecyl Dimethylbenzammonium chloride (32): Laurylpyridinium chloride (33): N- (3,4-dichlorophenyl) -N '-(4-
Chlorophenyl) urea (34): N- (3-trifluoromethyl-4-chlorophenyl) -N '-(4-chlorophenyl) urea (35): 3-hydroxy-5-methyl-isoxazole (36): D, L 2-benzylamino-1-propanol (37): 3-diethylamino-1-propanol (38): 2-dimethylamino-2-methyl-1-propanol (39): 3-amino-1-propanol (40) : Isopropanolamine (41): Diisopropanolamine (42): N, N-Dimethylisopropanolamine (43): N-lauryl-β-aniline The compounds preferably used in the above fungicide are thiazoline compounds and benzoic acid. An acid compound, a pyridine compound, a guanidine compound, and a quaternary ammonium compound. Furthermore, a thiazoline compound or a benzoic acid compound is particularly preferable.

The amount of the compounds (A) to (O) added is preferably 0.002 g to 50 g, and more preferably 0.005 g to 10 g, per liter of the stabilizing solution.

When a specific chelating agent is used in the stabilizing solution, the storage stability of the stabilizing solution is improved.

The chelating agent preferably used in the stabilizing solution is iron (III)
The chelate stability constant with an ion is 8 or more.

In the present invention, the chelate stability constant means the stability of a complex formed by a metal ion and a chelate in a solution, and means a constant defined as the reciprocal of the dissociation constant of the complex. Gee. siren. D. I. Martel (LGSillen.AEMartell), “Stability Constants Metallion Complex (Stability Co
nstants of Metalion Complexes) ”, The Chemical
Society London (The Chemical Society Londo
n) (1964), S. Chaberek., A. AEMartell, “Organic Sequesteri
ng Agents) "Wiley (1959) and the like, chelating agents having chelate stability constants with iron (III) ions of 8 or more include polyphosphates, aminopolycarboxylates, Oxycarboxylates, polyhydroxy compounds, organic phosphates, condensed phosphates and the like are used, and particularly when aminopolycarboxylates and organic phosphates are used, good results can be obtained. Examples of the chelating agent include, but are not limited to, the following.

One or two or more chelating agents may be used in combination, and the amount added may be in the range of 0.05 g to 40 g per stabilizer, preferably 0.1 to 20 g.

Among these chelating agents, diethylenetriaminepentaacetic acid and 1-hydroxyethylidene-1,1-diphosphonic acid are particularly preferably used.

The pH of the stabilizing solution is not particularly limited, but preferably pH 0.5 to 1
It is in the range of 2.0, more preferably in the range of pH 5.0 to 9.0, and particularly preferably in the range of pH 6.0 to 9.0.

The pH adjusting agent that can be contained in the stabilizing solution can be any of the commonly known alkali agents or acid agents, but it is preferable that the amount is small.

In addition to these, various stabilizer additives may be added to the stabilizer, and examples of these additives include optical brighteners, surfactants, organic sulfur compounds, onium salts, and formalin.

The treatment temperature for the stabilizing treatment is in the range of 15 ° C to 60 ° C, preferably 20 ° C to 45 ° C. Also, the processing time is preferably as short as possible from the viewpoint of rapid processing, but usually 20 seconds to 10
Minutes, most preferably 1 minute to 5 minutes, and in the case of stabilizing treatment in a plurality of tanks, it is preferable that the treatment is performed in a shorter time in the first-stage tank and longer in the second-stage tank. 20% to 50% of the previous tank
It is desirable to process sequentially with increased processing time.

Although the temperature of the drying step can be arbitrarily selected, it is preferably 50 ° C or higher, more preferably 70 ° C or higher.

The silver halide color photographic light-sensitive material according to the present invention includes an internal development method in which a color-forming agent is contained in the light-sensitive material (see US Pat. Nos. 2,376,679 and 2,801,171), and a color-forming agent is contained in the developer. External developing method (US Pat. No. 2,252,
No. 718, No. 2,592,243, No. 2,590,970)).

As the color former, any one generally known in the art can be used. For example, cyan color formers are those based on a naphthol or phenol structure to form an indoaniline dye by coupling, and magenta colorants are those having a 5-pyrazolone ring having an active methylene group as a skeleton structure, yellow color formers. Examples of the benzoylacetanilide having an active methylene chain, those having an acylacetanilide structure such as pivalylacetanilide having a substituent at the coupling position,
Any of those not possessed can be used. As described above, as the color former, both so-called 2-equivalent type coupler and 4-equivalent type coupler can be applied. The silver halide emulsion which can be used is any halogenated one such as silver chloride, silver bromide, silver iodide, silver chlorobromide, silver chloroiodide, silver iodobromide, silver chloroiodobromide or a mixture thereof. It may be one using silver. Further, as these silver halide protective colloids, natural products such as gelatin and various compounds obtained by synthesis can be used. The silver halide emulsion may contain usual photographic additives such as stabilizers, hardeners, sensitizing dyes and surfactants.

The silver halide photographic light-sensitive material of the present invention preferably has a colloidal silver dispersion layer. The colloidal silver dispersion layer may be a filter layer or an antihalation layer,
Further, it may be dispersed in the emulsion layer. As a method for producing these colloidal silver dispersions, Japanese Patent Publication No. 43-2774
No. 0, 49-43201, 45-14890, JP-A-51-89722.
No. 1 and British Patent No. 1,032,871 and the like, and synthesized by a general method.

(Effects of the Invention) As described above, according to the present invention, one of two light-sensitive materials of different types is processed in a color developing tank to which a color developing solution is replenished,
Since the other photosensitive material is subjected to color development processing by overflow from the color developing tank, the replenishing solution tank for the photosensitive material can be made common and the processing unit for the photosensitive material can be made compact, and the work space around the processing device can be reduced. It is easy to secure. Moreover, since the replenisher is used in common, the number of kinds of replenisher to be dissolved and prepared is reduced, so that the replenisher dissolving work can be simplified and the time required for the work can be shortened. Further, since the treatment device is not provided with a water washing treatment means, the drain pipe is not required to be installed, the installation place is not selected, and a large amount of water is not used, so that the cost is saved.

[Embodiment 1] FIG. 1 is a longitudinal sectional view of a processing device for a color negative film which is an embodiment of a processing system (a) of a processing device according to the present invention, and FIG. 2 is an example of the processing system (b). FIG. 3 is a vertical sectional view of a color paper processing apparatus as an embodiment, and FIG. 3 is a plan view of the processing apparatus in which the two processing apparatuses shown in FIGS. 1 and 2 are arranged in parallel and close to each other.

In the figure, reference numeral 1 is a mounting portion for mounting a roll 3 wound by connecting a color negative film 2 which has been photographed or a magazine 3 accommodating a color paper 22, and an automatic developing machine main body 4A for color negative film or an automatic developing machine for color paper. It is provided on the side wall of the developing device main body 4B.

Color negative film 2 of the magazine attached to the mounting part 1
Alternatively, the color paper 22 is fed from the main body entrance portion 5 to the main body 4A or
4B, the color negative film 2 is automatically passed through the color developing tank 6, the bleaching tank 7, the fixing tank 8, the first stabilizing first tank 9A, the first stabilizing second tank 9B, and the second stabilizing tank 10. After being subjected to development processing, it is dried in the drying section 14 (having an openable / closable lid), taken out from the outlet 16 of the main body, and then wound by a winder.
The color paper 22 is processed in the same manner as a negative film through the color developing tank 11, the bleach-fixing tank 12, the first stabilizing first tank 13A, the first stabilizing second tank 13B, and the first stabilizing third tank 13C. , It is cut and discharged from the outlet. A roller 15 for conveying a color negative film or a color paper is provided in each tank, and a predetermined process is performed while the color negative film 2 or the color paper 22 is immersed in a liquid. An open / close lid is provided on each of the tanks 6 to 10 and 11 to 13C so as to prevent evaporation and to perform maintenance.

Color developing tank of automatic developing machine for color paper in each tank 11
And the color developing tank 6 of the automatic processor for color negative film,
The liquid level is changed and connected so that the overflow of the color developing tank 11 flows into the color developing tank 11, the replenisher is replenished in the color developing tank 6, and the overflow of the color developing tank 11 is discharged to the outside of the tank. . Further, the first stabilizing first tank 9A and the second tank 9B of the color negative film automatic developing machine, and the first stabilizing first tank 13A, the second tank 13B and the third tank 13C of the color paper automatic developing machine, respectively. Overflow from the second tank 9B to the first tank 9A or from the third tank 13C to the second tank 13B, the second tank 13
The liquid level is changed so that it flows from B to the first tank 13A, the replenisher is replenished to the second tank 9B and the third tank 13C, and the overflow of the first tank 9A and the first tank 13A It is discharged outside the tank.

The automatic developing machine of this embodiment is provided with a cooling chamber 17 adjacent to the color developing tank 6 or 11. A fan 18 is provided on the outer wall of the cooling chamber 17, and an appropriate number of outside air introducing holes 19 are also provided. The cooling chamber 17 also serves as a control system device chamber and houses a control unit 21. The control unit 21 controls the large-capacity electric heater 22 and the small-capacity electric heater according to the liquid temperature input signal of the color developing tank 6 or 11 detected by the temperature sensor 20.
23 is ON-OFF controlled to control the temperature for heating, and the fan 18 is also ON-OFF controlled to control the temperature for cooling.

In the figure, reference numeral 24 denotes a liquid circulation agitator housed in the cooling room 17 which also serves as a control system equipment room, and a liquid feed pump 26 and a liquid are provided in the middle of a passage 25 connecting the upper part and the lower part of the color developing tank 6 or 11. A cleaning filter 27 is provided. Reference numerals 28 and 125 denote blades or squeeze portions formed by a pyramid-shaped blade plate or the like, which effectively prevents carry-in of the liquid from the previous bath to the next bath.

In the drawing, 29A, 29B, 30A and 30B indicate waste liquid tanks, and 29A is color developer 1 bleaching solution and 2nd stabilizing solution is 29B.
The fixing solution and the first stabilizing solution flow into 30A, the color developing solution into 30B, and the bleach-fixing solution and the first stabilizing solution flow into 30B.

In the processing apparatus of the present invention, as shown in FIG. 3, an automatic developing machine 4A for color negative film and an automatic developing machine 4B for color paper are installed back to back as shown, and processing tanks 7, 8, 9B, Replenisher is supplied to 10, 11, 12 and 13C from the replenisher tanks 31, 32, 33, 34, 35, 36 and 37, respectively, which are contained in the processing tanks 6, 9A, 13A and 13C. No replenisher is supplied, the overflow of the processing tank 11 to the processing tank 6, the overflow of the processing tank 9B to the processing tank 9A, and the processing tank 9A.
The overflow of 13C is connected to the processing tank 13B, and the overflow of the processing tank 13B is connected to the processing tank 13A.

Note that 38, 39, 40, 41, 42, 43, and 44 represent insertion ports for inserting the replenishment agent kit.

(Experiment 1) A color negative film and a color paper were self-made in the following procedure.

An antihalation layer and a gelatin layer are provided on a triacetate film base, and a red-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, a filter layer containing yellow colloidal silver, and a blue-sensitive silver halide emulsion layer are formed on the triacetate film base. Was coated so that the amount of silver was 70 mg per 100 cm ² . The above emulsion layer is silver iodobromide having a mol% of silver iodide of about 4.5%. In this case, α- (4-nitrophenoxy) -α-pivalyl was used as a yellow coupler in the blue-sensitive silver halide emulsion layer. -5
[Γ- (2,4-di-t-aminophenoxy) butyramide] -2-chloroacetanilide was used, and the green-sensitive silver halide emulsion layer contained 1- (2,4,
6-trichlorophenyl) -3-{[α- (2,4-di-t
-Amylphenoxy) -acetamide] benzamide}
-3-Pyrazolone and 1- (2,4,6-trichlorophenyl) -3-{[α- (2,4-di-t-amylphenoxy) -acetamido] benzamide} -4- (4-methoxyphenylazo ) -5-Pyrazolone and 1-hydroxy-N- {α- (2,4-di-t-amylphenoxy) as a cyan coupler for the red-sensitive silver halide emulsion layer.
Butyl} -2-naphthamide was used, and additives such as a sensitizing dye, a hardener and a spreader were added to each emulsion layer.
In this way, a color negative film sample was prepared and cut into 24 sheets (373 cm ² ).

As a coupler on a resin-coated paper support, 2- (1-benzyl-2,4-dioxyimidazolidin-3-yl) -2-pivalyl-2'-chloro-
5 '-[4- (2,4-di-t-pentylphenoxy) butanamide] acetanilide was dissolved in dibutyl phthalate, protected and dispersed in an aqueous gelatin solution, and then mixed with a silver chlorobromide emulsion for coating. The coating amount of the coupler and silver used at this time per 100 cm ² was 24 mg of the coupler and 2.85 mg of silver. A gelatin intermediate layer containing dioctylhydroquinone was provided on top of this, and a 3- {2
-Chloro-5- [1- (octadecyl) succinimide] anilino} -1- (2,4,6-trichlorophenyl)
-5-Pyrazolone was dissolved in dibutyl phthalate, protected and dispersed in a gelatin aqueous solution, mixed with a green light-sensitive silver chlorobromide emulsion, and then dried by coating. The amount of coupler used at this time was 49 mg and silver was 2.87 mg per 100 cm ² . On this layer, a gelatin solution of dioctylhydroquinone was applied as a color turbidity preventing layer, and further on this layer, 2- [2- (2,4-di-t-pentylphenoxy) butanamide] -4 was used as a coupler. , 6-dichloro-5-
Methylphenol was dissolved in dibutyl phthalate, protected and dispersed in an aqueous gelatin solution, mixed with a red light-sensitive silver chlorobromide emulsion, and then dried by coating. The coating amount of the coupler used at this time was 30 mg per 100 cm ² , and the amount of silver was 1.75 mg.

A color paper sample was prepared as described above and cut to a width of 8.25 cm.

The photographed color negative film was processed and printed on a color paper in an E size size for processing. The first to the processing
Processing was performed according to the processing steps shown below using the automatic processor shown in FIG.

(Color negative treatment) Treatment process Treatment temperature (℃) Treatment time 1 Color development 38.0 3 minutes 15 seconds 2 Bleach 38.0 4 minutes 3 Fixed 38.0 3 minutes 15 seconds 4 1st stability 32.0 2 minutes 5 2nd stability 32.0 1 minutes ( Color paper treatment) Treatment process Treatment temperature (° C) Treatment time 1 Color development 38.0 3 minutes 15 seconds 2 Bleach fixing 38.0 1 minute 30 seconds 3 First stability 32.0 3 minutes The composition of the treatment liquid used is as follows.

The color developing replenisher is replenished in a 1.8 ml color developing bath per 100 cm ^{2 of} color paper, the bleach replenisher is replenished in an 18 ml bleaching bath per 100 cm ^{2 of} color negative film, and the fixing replenisher is
Color negative film 100 cm ² per 7 ml fixing bath is replenished,
Furthermore, the first stable replenisher is 100 cm ^{2 of} color negative film.
Supplemented to per 10ml first stabilizing bath, the second stabilizing replenisher is replenished in the color negative film 100 cm ² per 10ml second stabilizing bath, a bleach-fixing solution replenisher, color paper 100 cm ² per 1.
It is replenished in 0 ml bleach-fix bath and the first stable replenisher is replenished in ² ml per 100 cm ² of color paper. The processing amount was 30 shots of 24 sheets of the above color negative film per day, and an average of 25 sheets of E size paper was processed per one sheet of this color negative film. This treatment was continuously performed for 7 days.

(Experiment 2) The color negative film and color paper used, the automatic processor, the processing step, the processing solution, the processing amount and the number of processing days were exactly the same as in Experiment 1, except that 0.5 g of potassium bromide was added to the color development replenisher. / l was added. At this time, in order to maintain the same finish as in Experiment 1, the replenisher amount of the color developing replenisher was changed to 3.4 ml per 100 cm ² of color paper.

(Experiment 3) Similar to Experiment 2, 0.6 g / l of potassium bromide was added during the replenishment of the color developing solution. At this time, in order to maintain the same finish as in Experiment 1, the replenisher amount of the color developing replenisher was changed to 4.4 ml per 100 cm ² of color paper.

(Experiment 4) The color developing solution tanks of the automatic developing machine used in Experiments 1 to 3 were separated from each other, and a replenisher tank for replenishing the color developing layer with a replenisher was installed in the color negative film automatic developing machine. For this reason, the automatic processor for color negative is enlarged by the amount of the replenisher tank and replenisher installed. These completely separated automatic processors for color negative film and color paper were used and processed in the same processing step using the same light-sensitive material as used in Experiments 1 to 3. The processing solutions used were the same as those used in Experiments 1 to 3 except that the color developing solution for color negative film and the replenishing solution were different as shown below.

Color development replenisher is 15 ml per 100 cm ^{2 of} color negative film.
The color developing layer was replenished.

The replenishment amount, the treatment amount, and the treatment days of the other treatment solutions were exactly the same as in Experiment 1.

After all the experiments were completed, the amount of the color developing replenisher and the number of dissolutions were compared. The results are shown in Table 1.

However, the color developing replenisher tank built in the automatic developing machine for color paper used in Experiments 1 to 3, the color developing replenishing solution tank built in the automatic developing machine for color paper used in Experiment 4, and the automatic development for color negative film. The capacity of the color developing replenisher tank built into the machine was 10 l.

When the processing of the present invention is performed by the automatic processor of the present invention,
Since there is only one type of color developing replenisher, the dissolving work is not confusing and easy, and the automatic developing machine is small and the work is easy. Also, sometimes the concentration of B ions in the replenisher is
When the amount was 4.2 × 10 ^-3 mol or less, the amount of the replenisher was smaller than that of the comparative example, and the number of times of dissolution was small, which was extremely good.

[Example 2] 3-methyl-4-amino-N-ethyl-N- (2-methoxyethyl) -m-toluidine-di-paratoluene sulfone was used as the color developing agent in Experiments 1, 2, and 3 of Example 1. Approximately similar results were obtained with the change to the acid salt.

[Brief description of drawings]

FIG. 1 shows a processing system (a) constituting the processing apparatus of the present invention.
FIG. 2 is a vertical sectional view of a color negative film processing apparatus which is an example of the present invention, FIG. 2 is a vertical sectional view of a color paper processing apparatus which is an example of the processing system (b), and FIG. It is a top view which shows one Example of the processing apparatus of this invention which installed the two processing apparatuses shown in FIG. 2 and FIG. 2 in parallel. 4A …… Main body of automatic developing machine for color negative film 4B …… Main body of automatic developing machine for color paper 6 …… Color developing tank, 7 …… Bleaching tank 11 …… Color developing tank

Claims (5)

[Claims] 1. A silver halide color photographic light-sensitive material having two different types in a processing method in which a silver halide color photographic light-sensitive material is processed by an automatic processor in which a processing solution is replenished in a processing tank for development processing. At least two color developing tanks for the material are provided, one of which is replenished with a replenisher according to the processing amount of the color photographic light-sensitive material, and the other of which is replenished with the liquid of the color developing tank. A characteristic method for processing a color photographic light-sensitive material. 2. A color developing tank comprising a plurality of color developing tanks, and a replenishing solution according to a processing amount is replenished to the other color developing tanks, and an overflow of the color developing tank is replenished to the other tanks. A method for processing a color photographic light-sensitive material according to item 1. 3. A color photograph according to claim 1 or 2, wherein the different types of silver halide color photographic light-sensitive materials are a color negative light-sensitive material for photographing and a color positive light-sensitive material for printing. Method of processing photosensitive material. 4. The replenisher for the color developing tank has a Br ⁻ ion concentration of 4.2 × 10 ⁻³ mol / l or less, as defined in claim 1, claim 2, or claim 3. A method for processing a color photographic light-sensitive material as described above. 5. A processing system (a) comprising a color developing tank, a tank having a bleaching function, a fixing tank and a stabilizing solution tank and not having a washing tank for washing a light-sensitive material processed with running water, and a color developing tank. The color of the processing system (b) is provided in parallel with and in close proximity to the processing system (b) which has a bleaching tank and a stabilizing solution tank, and does not have a washing tank for washing photosensitive materials processed with running water. The color developing replenisher is replenished to the developing tank, and the overflow of the color developing tank is connected to the color developing tank of the processing system (a). An apparatus for processing a color photographic light-sensitive material, characterized in that means for replenishing the same is not provided.