JPH04274237A - Method for processing silver halide color photosensitive material - Google Patents

Abstract

PURPOSE:To reduce replenishing quantity and the quantity of waste liquid by composing a replenishing liquid for a bleaching fixer of two or more kinds of enriched liquid parts, and directly replenishing it into a bleaching-fixing tank without previously mixing the above parts for highly enriching the bleaching fixer. CONSTITUTION:After exposing silver halide color photosensitive material preferably containing at least one layer of a high silver chloride emulsion having above 90mol% of chlorine ion, color development, bleaching-fixing and water washing or stabilizing treatment are executed. In these continuous processes, a replenishing liquid for a bleaching fixer is composed of two or more kinds of enriched liquid parts, for instance three enriched liquid parts prepared from a bleaching agent, a fixer and acid by applying them as each main component, and directly replenished into a bleaching-fixing tank without previously mixing each enriched liquid with the unit processing quantity of the sensitive material.

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 silver halide color photographic light-sensitive materials, and more particularly to a method for replenishing a bleach-fix solution that significantly reduces the amount of waste solution.

0002

[Prior Art] When processing silver halide color photographic materials continuously, the most commonly used method is to add a certain amount of replenisher to the processing tank for a certain amount of processing to maintain processing performance. It is true.

[0003] By the way, when the processing tank is replenished with the replenishing liquid, a portion of the tank liquid is naturally discharged, and this is called overflow liquid. Since this overflow liquid is generally discarded, it is preferable for the amount of liquid to be discarded to be as small as possible from the viewpoint of environmental issues and cost performance.

[0004] Therefore, in the bleach-fix solution, a recycling technique for reusing the overflow solution as a replenisher was proposed in Japanese Patent Application Laid-open No. 48.
It is disclosed in No. 49437 and No. 50-145231. However, this method requires space to temporarily store the overflow liquid, and
It is necessary to add various chemicals for regeneration, and the operation is relatively difficult, so it cannot be used in all photo labs, and an easy method to reduce the amount of waste liquid has been awaited.

[0005] Furthermore, a technique for replenishing the bleach-fix solution by dividing it into two parts is disclosed in JP-A-55-79446, but the present invention achieves higher concentration than the disclosed technique, and reduces the amount of replenishment and waste liquid. The aim is to reduce the

[0006] Accordingly, the present invention discloses a technique that significantly reduces the amount of replenishment of the bleach-fix solution and, as a result, significantly reduces the amount of waste solution.

It has been found that the above object can be achieved by using the following technique. That is, [Item 1] After exposing a silver halide color photographic light-sensitive material, in the continuous processing step of color development, bleach-fixing, and water washing or stabilization treatment, the bleach-fix replenisher is
A silver halide color photographic light-sensitive material comprising more than one concentrate part, characterized in that each concentrate part is directly replenished into a bleach-fixing tank without being mixed in advance for the unit processing amount of the light-sensitive material. Processing method [Item 2] The silver halide color photographic light-sensitive material according to item 1 above, wherein the bleach-fix replenisher consists of three concentrated liquid parts each containing a bleach, a fixing agent, and an acid as main components. processing method. [Item 3] Processing of the silver halide color photographic light-sensitive material according to the above item 2, wherein the silver halide color photographic light-sensitive material contains a high silver chloride emulsion containing 90 mol % or more of chloride ions in at least one layer. Method.

[0008] The processing of the present invention will be explained in detail below. In the present invention, the light-sensitive material is subjected to color development, bleach-fixing, and water washing (or stabilization treatment).

The color developer used in the present invention contains:
Contains a known aromatic primary amine color developing agent. Preferred examples are p-phenylenediamine derivatives, typical examples include N,N-diethyl-p-phenylenediamine, 2-amino-5-diethylaminotoluene, 2-
Amino, 5-(N-ethyl-N-laurylamino)toluene, 4-[N-ethyl-N-(β-hydroxyethyl)amino]aniline, 2-methyl-4-[N-ethyl-
N-(β-hydroxyethyl)amino]aniline, 4-
Amino-3-methyl-N-ethyl-N-[β-(methanesulfonamido)ethyl]-aniline, N-(2-amino-5-diethylaminophenylethyl)methanesulfonamide, N,N-dimethyl-p- Phenylenediamine, 4-amino-3-methyl-N-ethyl-N-methoxyethylaniline, 4-amino-3-methyl-N-ethyl-N-β-ethoxyethylaniline, 4-amino-3-
Examples include methyl-N-ethyl-N-β-ptoxyethylaniline. Particularly preferably 4-amino-
3-Methyl-N-ethyl-N-[β-(methanesulfonamido)ethyl]-aniline. Also, these p
- The phenylenediamine derivative may be a salt such as a sulfate, a hydrochloride, a sulfite, or a p-toluenesulfonate. The amount of the aromatic primary amine developing agent used is preferably in a concentration of about 0.1 g to about 20 g, more preferably about 0.5 g to about 10 g per liter of color developer.

In carrying out the present invention, it is preferable to use a color developer that does not substantially contain benzyl alcohol in view of the working environment. Here, "substantially not containing" means a benzyl alcohol concentration of preferably 2 ml/liter or less, more preferably 0.5 ml/liter or less, and most preferably no benzyl alcohol at all.

The color developer used in the present invention must be substantially free of sulfite ions in order to suppress fluctuations in photographic properties due to continuous processing (substantially free of sulfite ions herein means sulfite ion concentration of 3 .0×10 −3 mol/liter or less) is more preferable. Most preferably, it does not contain any sulfite ions. However, here,
In the present invention, a very small amount of sulfite ion used to prevent oxidation in a processing agent kit in which the developing agent is concentrated before being mixed into a solution for use is excluded.

The color developer used in the present invention preferably does not substantially contain sulfite ions, but may further contain substantially hydroxylamine in order to suppress fluctuations in photographic properties due to fluctuations in hydroxylamine concentration. It is more preferable that the hydroxylamine concentration is not more than 5.0×10 −3 mol/liter. Most preferably it does not contain any hydroxylamine.

The color developer used in the present invention preferably contains an organic preservative instead of the hydroxylamine or sulfite ion. The term "organic preservative" as used herein refers to any organic compound that reduces the rate of deterioration of an aromatic primary amine color developing agent when added to a processing solution for a color photographic light-sensitive material. In other words, they are organic compounds that have the function of preventing the oxidation of color developing agents due to air, etc. Among them, hydroxylamine derivatives (excluding hydroxylamine), hydroxamic acids, hydrazines, hydrazides, phenols, α-hydroxy Ketones, α
-aminoketones, sugars, monoamines, diamines,
Particularly effective organic preservatives include polyamines, quaternary ammonium salts, nitroxy radicals, alcohols, oximes, diamide compounds, and fused cyclic amines. These are Japanese Patent Publication No. 48-30496 and Japanese Patent Publication No. 52-1
No. 43020, No. 63-4235, No. 63-3084
No. 5, No. 63-21647, No. 63-44655,
No. 63-53551, No. 63-43140, No. 63
-56654, 63-58346, 63-43
No. 138, No. 63-146041, No. 63-4465
No. 7, No. 63-44656, U.S. Patent No. 3,615,
No. 503, No. 2,494,903, JP-A-1-979
No. 53, No. 1-186939, No. 1-186940, No. 1-187557, No. 2-306244, etc. As other preservatives, JP-A-57-4
Various metals described in No. 4148 and No. 57-53749, salicylic acids described in JP-A-59-180588,
JP-A-63-239447, JP-A-63-12834
No. 0, JP-A-1-186939 and JP-A-1-187557
Amines such as those described in JP-A-54-3532
Alkanolamines described in JP-A-56-9434
Polyethyleneimines described in No. 9, U.S. Patent No. 3,74
Aromatic polyhydroxy compounds described in No. 6,544 and the like may be used as necessary. In particular alkanolamines such as triethanolamine, dialkylhydroxylamines such as N,N-diethylhydroxylamine and N,N-di(sulfoethyl)hydroxylamine, N
, N-bis(carboxymethyl)hydrazine (excluding hydrazine), or an aromatic polyhydroxy compound typified by sodium catechol-3,5-disulfonate.

In particular, it is more preferable to use dialkylhydroxylamine and/or hydrazine derivatives in combination with alkanolamines in terms of improving the stability of the color developer and also improving the stability during continuous processing. .

In the present invention, it is preferred that the color developer contains 3.0 x 10-2 to 1.5 x 10-1 mol/liter of chlorine ions. Particularly preferably, 3.5×
It is 10-2 to 1×10-1 mol/liter. If the chloride ion concentration is more than 1.5 x 10-1 to 10-1 mol/liter, it has the disadvantage of delaying development, which is not preferable in achieving the object of the present invention of rapid development and high maximum concentration. . Moreover, if it is less than 3.0×10 −2 mol/liter, it is not preferable in terms of preventing fogging. In the present invention, 3.0 x 10-bromine ions are added to the color developer.
The content is preferably 5 mol/liter to 1.0×10 −3 mol/liter. More preferably, 5.0×10
-5 to 5 x 10-4 mol/liter. If the bromide ion concentration is greater than 1 x 10-3 mol/liter, development will be delayed, maximum density and sensitivity will be reduced, and 3.0 x 10-
If it is less than 5 mol/liter, fogging cannot be sufficiently prevented.

The chlorine ions and bromine ions may be added directly to the color developer, or may be eluted from the light-sensitive material into the color developer during the development process. When added directly to the color developer, chloride ion supplying materials include sodium chloride, potassium chloride, ammonium chloride, lithium chloride, magnesium chloride, and calcium chloride. Alternatively, it may be supplied from an optical brightener added to the color developer. As a supply material for bromide ions,
Examples include sodium bromide, potassium bromide, ammonium bromide, lithium bromide, calcium bromide, and magnesium bromide. When eluted from a light-sensitive material during development processing, both chloride ions and bromine ions may be supplied from the emulsion.
It may be supplied from sources other than emulsions.

[0017] The color developer used in the present invention preferably has a pH of 9 to 12, more preferably 9 to 11.0, and the color developer may contain other known developer component compounds. be able to. In order to maintain the above pH, it is preferable to use various buffers. As buffering agents) carbonate, phosphate, borate, tetraborate, hydroxybenzoate, glycyl salt, N,N-dimethylglycine salt, leucine salt, norleucine salt, guanine salt,
3,4-dihydroxyphenylalanine salt, alanine salt, aminobutyrate, 2-amino-2-methyl-1,3-propanediol salt, valine salt, proline salt, trishydroxyaminomethane salt, lysine salt, etc. can be used. can. 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 have no effect on photographic performance. It is particularly preferable to use these buffers because they have the advantages of having no adverse effects (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, and 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-2
-potassium hydroxybenzoate (potassium 5-sulfosalicylate), and the like. The amount of the buffer added to the color developer is preferably 0.1 mol/liter or more, particularly 0.1 mol/liter to 0.4 mol/liter.
Particular preference is given to moles/liter.

In addition, various chelating agents can be used in the color developer as agents for preventing precipitation of calcium and magnesium, or in order to improve the stability of the color developer. For example, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, ethylenediaminetetraacetic acid, N,N,N-trimethylenephosphonic acid, ethylenediamine-N,N,N
',N'-tetramethylenephosphonic acid, transsilohexanediaminetetraacetic 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-N,N'-diacetic acid, hydroxyethyliminodiacetic acid, and the like. Two or more of these chelating agents may be used in combination, if necessary. These chelating agents may be added in an amount sufficient to sequester metal ions in the color developer. For example 1
It is about 0.1g to 10g per liter.

[0020] Any development accelerator can be added to the color developer if necessary. As a development accelerator,
-16088, 37-5987, 38-782
6, No. 44-12380, No. 45-9019, and U.S. Pat. No. 3,813,247, etc.;
-15554, p-phenylenediamine compounds, JP-A-50-137726, JP-B-1987-3
No. 0074, JP-A-56-156826 and JP-A No. 52-
Quaternary ammonium salts represented by No. 43429 etc., U.S. Patent Nos. 2,494,903 and 3,128,182
No. 4,230,796, No. 3,253,919, Japanese Patent Publication No. 41-11431, U.S. Patent No. 2,482,
No. 546, No. 2,596,926 and No. 3,582,
Amine compounds described in No. 346 etc., Japanese Patent Publication No. 37-16
No. 088, No. 42-25201, U.S. Patent No. 3,12
No. 8,183, Special Publication No. 41-11431, No. 42-2
Polyalkylene oxides such as those disclosed in US Pat. No. 3,883 and US Pat. No. 3,532,501, 1-phenyl-3-pyrazolidones, imidazoles, etc. can be added as necessary. Benzyl alcohol is as described above.

In the present invention, any antifoggant can be added if necessary. As antifoggants, alkali metal halides such as sodium chloride, potassium bromide, potassium iodide, and organic antifoggants can be used. Examples of organic antifoggants include benzotriazole, 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. The color developer applicable to the present invention preferably contains an optical brightener. As the fluorescent brightener, 4,4'-diamino-2,2'-disulfostilbene compounds are preferred. The amount added is 0-5g/liter, preferably 0.1g-
4/liter. Further, various surfactants such as alkylsulfonic acid, arylsulfonic acid, aliphatic carboxylic acid, and aromatic carboxylic acid polyalkyleneimine may be added as necessary.

The processing temperature of the color developer applicable to the present invention is 20 to 50°C, preferably 30 to 40°C. The treatment time is 20 seconds to 5 minutes, preferably 30 seconds to 2 minutes. It is preferable that the captured amount is small, but 20 to 600 ml is appropriate per m2 of photosensitive material, preferably 50 ml.
-200 ml, more preferably 60 ml - 150 ml.

Next, a bleach-fix solution is used in the desilvering step of the present invention. The bleach-fix replenisher of the present invention consists of two or more concentrate parts. Preferably it consists of three concentrate parts.

One of the concentrate parts is based on bleach. As the bleaching agent, any bleaching agent can be used, but especially organic complexes of iron (III) (e.g. ethylenediaminetetraacetic acid, diethylenetoeiaminepentaacetic acid, 1
, 3-propanediaminetetraacetic acid, methyliminodiacetic acid,
(iminodiacetic acid, cyclohexanediaminetetraacetic acid, glycol ether diaminetetraacetic acid, etc.) are preferred. These compounds include sodium salts, potassium salts, lithium salts,
Various salts such as ammonium salts may be formed, and ammonium salts are particularly preferably used for the purpose of making a highly concentrated solution. These ferric complex salts may be used in the form of complex salts, or ferric salts such as ferric sulfate, ferric chloride, ferric nitrate,
A ferric complex salt may be formed in a solution using ferric ammonium sulfate, ferric phosphate, etc., and a chelating agent such as aminopolycarboxylic acid. Further, the chelating agent may be used in excess of the amount required to form the ferric salt.

[0025] The concentration of bleach in the concentrate part is 0.3 to 1.
．． The amount is 5 mol/liter, preferably 0.4 to 1.0 mol/liter. The pH is 1-9, preferably 2-7. If the pH is too low, the solubility will decrease, and if the pH is too high, the decomposition reaction will be accelerated, both of which are unfavorable.

[0026] Another concentrate part includes a part whose main component is a fixing agent. As the fixing agent used in the present invention, any known fixing compound can be used. Among them, thiosulfates such as sodium thiosulfate and ammonium thiosulfate, thiocyanates such as sodium thiocyanate and potassium thiocyanate, thioether compounds such as ethylenethiobisglycolic acid and 3,6-dithia-1,8-octanediol. , thioureas, and mesoionic compounds described in Japanese Patent Application No. 1-314974 are preferred. In particular, it is preferable to use ammonium thiosulfate because it can be highly concentrated and liquefied and has an excellent fixing speed. The concentration of the fixing agent per liter of concentrate is 2 to 6 mol/liter, preferably 3 to 5 mol/liter.

It is preferable that the concentrate part of the fixing agent further contains a preservative. Preservatives include sulfites (e.g. sodium sulfite, potassium sulfite, ammonium sulfite), bisulfites (e.g. ammonium bisulfite, sodium bisulfite, potassium bisulfite), metabisulfites (e.g. potassium metabisulfite, It is preferred to contain a sulfite ion releasing compound such as sodium metabisulfite, ammonium metabisulfite). In addition, as preservatives, benzenesulfinic acids, ascorbic acids,
Carbonyl bisulfite adducts and the like can be used. The concentration of preservative in the concentrate is 0.5 to 4 mol, preferably 1.0 to 3 mol per liter.

In the present invention, in addition to the above two concentrated liquid parts, it is preferable to use a third concentrated liquid part that further contains an acid in order to increase the concentration ratio of the other two parts. Further, in order to reduce the amount of replenishment of each concentrate part as much as possible, the presence of this part is important because it is necessary to neutralize the increase in pH caused by the color developer brought in from the previous bath. Acids used include acetic acid, citric acid,
Organic acids such as oxalic acid, succinic acid, propionic acid, hydrochloric acid,
Although various acids such as inorganic acids such as sulfuric acid, nitric acid, and phosphoric acid can be used, acetic acid and nitric acid are preferable from the viewpoint of safety and cost. If the concentration of acid in the concentrated solution can be managed from a safety standpoint, it is preferable that the acid concentration be higher, since the amount of replenishment can be reduced. 10% to 100%, preferably 20% per liter of concentrate
~80%.

In the present invention, it is preferable that the amount of replenishment of each concentrated solution is small.
The total amount of replenishment for each part is 10 ml to 40 ml, preferably 15 ml to 35 ml. This amount is smaller than the conventional replenishment amount of 50ml to 350ml,
As a result, the amount of waste liquid is also significantly reduced. Further, the pH of the tank liquid is preferably controlled to pH 4 to 7, more preferably 5 to 6.5, from the viewpoint of speed and image storage stability.

The bleach-fixing solution of the present invention may contain a bleach accelerator, if necessary. For example, US Patent 3
, 893,858, German Patent No. 1,290,
Compounds having a mercapto group or disulfide bond described in JP-A No. 812, JP-A-53-95630, Research Disclosure No. 17129 (July 1978 issue), JP-A No. 45-8506, JP-A-Sho. 52-
No. 20832, No. 53-32735, U.S. Patent No. 3,7
Thiourea compounds described in No. 06,561 and halides such as iodine and bromide ions are preferred because they have excellent bleaching power.

In addition, the bleach-fix solution that can be applied to the present invention contains bromides (such as potassium bromide, ammonium bromide,
sodium bromide) or chlorides (e.g. potassium chloride, ammonium chloride, sodium chloride) or iodides (
Rehalogenating agents such as potassium iodide, ammonium iodide, sodium iodide) can be included. If necessary, one or more inorganic acids or organic acids having a pH buffering capacity such as borax, sodium metaborate, sodium acetate, sodium carbonate, sodium phosphate, sodium citrate, and their alkali metal or ammonium salts, ammonium nitrate, or guanidine. It is possible to add corrosion inhibitors such as.

The concentrate part of the bleach-fix replenisher of the present invention is separately replenished directly into the tank liquor. The method of replenishing by mixing concentrated liquid parts cannot be used in this replenishment method because it may cause precipitation or deterioration of the liquid. The total amount of replenishment for each part is as described above, but for each part, it is about 3 to 15 ml per 1 m2 of photosensitive material, and it is preferable to replenish at a position as close as possible to the circulation path in the processing tank, and away from the overflow port. A more preferable position is

In the present invention, washing and/or stabilization treatment is generally performed after the bleach-fixing step.

The amount of washing water in the washing process depends on the characteristics of the photosensitive material (for example, depending on the materials used such as couplers), the purpose, the washing water temperature, the number of washing tanks (number of stages), the replenishment method such as countercurrent or forward flow, etc.
It can be set in a wide range depending on various other conditions. Among these, the relationship between the number of flushing tanks and the amount of water in the multistage countercurrent method is described in the Journal of the Society of Motion Picture and Television Engineers.
of Motion Picture and
Television Engineers) No. 64
Volume, p. 248-253 (May 1955 issue). Generally, the number of stages in the multistage countercurrent system is preferably 2 to 6, particularly preferably 2 to 4.

According to the multi-stage countercurrent method, the amount of washing water can be greatly reduced, for example, from 0.5 liters to less than 1 liter per 1 m2 of photosensitive material, and the effect of the present invention is remarkable. The increased residence time of water causes problems such as bacteria propagation and the resulting floating matter adhering to the photosensitive material. As a solution to such problems, the method of reducing calcium and magnesium described in JP-A-62-288838 can be used very effectively. In addition, isothiazolone compounds and thiabendazoles described in JP-A No. 57-8542, JP-A No. 61-12014
Chlorine-based disinfectants such as chlorinated sodium isocyanurate described in No. 5, benzotriazole described in JP-A No. 61-267761, copper ions, etc. "Chemistry of antibacterial and anti-mildew" by Hiroshi Horiguchi (1986) Sankyo Publication, Sanitation Technology Society (ed.) "Microbial Sterilization, Sterilization, and Anti-Mold Techniques" (1982) Industrial Technology Society,
“Encyclopedia of Antibacterial and Antifungal Agents” edited by the Japan Antibacterial and Antifungal Society (1986)
It is also possible to use the disinfectants described in .

Furthermore, in the washing water, a surfactant as a draining agent and a chelating agent typified by EDTA as a water softener can be used.

[0037] The above-mentioned water washing step can be followed or the stabilizing solution can be directly treated without going through the water washing step. A compound having an image stabilizing function is added to the stabilizing solution, such as an aldehyde compound typified by formalin, a buffer for adjusting the membrane pH suitable for dye stabilization, and an ammonium compound. Further, in order to prevent the proliferation of bacteria in the liquid and to impart anti-mold properties to the photographic material after processing, the various disinfectants and anti-mold agents described above can be used.

[0038] Furthermore, surfactants, optical brighteners, and hardeners can also be added. In the processing of the photosensitive material of the present invention, when stabilization is performed directly without going through a water washing step,
JP-A-57-8543, JP-A No. 58-14834, JP-A No. 6
All known methods described in Japanese Patent No. 0-220345 and the like can be used. In addition, it is also a preferable embodiment to use chelating agents such as 1-hydroxyethylidene-1,1-diphosphonic acid and ethylenediaminetemethylenephosphonic acid, and magnesium and bismuth compounds.

A so-called rinsing solution is also used as a washing solution or a stabilizing solution used after the desilvering treatment. The preferred pH of the water washing step or stabilization step is 4 to 10, more preferably 5 to 8. Although the temperature can be set variously depending on the use and characteristics of the photosensitive material, it is generally 15 to 45°C, preferably 20 to 4°C. Although the time can be set arbitrarily, a shorter time is preferable from the viewpoint of reducing processing time. Preferably 15 seconds to 1 minute 45 seconds, more preferably 30 seconds to 1 minute 30 seconds
Seconds.

[0040] The smaller the amount of replenishment in the water washing step or the stabilization step, the better from the viewpoints of running costs, reduction in the amount of piles removed, ease of handling, and the like. A specific preferable replenishment amount is 0.5 to 50 times, preferably 3 to 40 times, the amount brought in from the previous bath per unit area of the photosensitive material. Alternatively, the amount is 1 liter or less, preferably 500 ml or less per m2 of photosensitive material. Further, replenishment may be performed continuously or intermittently. The liquid used in the water washing and/or stabilization step can also be used in the previous step. As an example of this, a multi-stage counter-current system is used to reduce the overflow of the washing water into a bleach-fix bath, which is a pre-bath, and fill the bleach-fix bath with concentrated liquid.
One example is to reduce the amount of waste liquid.

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, as well as the processing method and processing additives applied to process this sensitive material, are as follows: , the following patent publications, especially European Patent EP 0,355,660A2 (Patent Application No.
107011) are preferably used.

[0042]

[Table 1]

[0043]

[Table 2]

[0044]

[Table 3]

[0045]

[Table 4]

[0046]

[Table 5]

[0047] Also, as a cyan coupler, JP-A-2-
In addition to the diphenylimidazole cyan coupler described in No. 33144, Ogawa Patent EP 0,333,185A2
3-hydroxypyridine cyan coupler (
Among them, 4 of couplers (42) listed as specific examples
Particularly preferred are equivalent couplers with a chlorine leaving group to make them di-equivalent, couplers (6) and (9), and cyclic active methylene cyan couplers described in JP-A No. 64-32260 (especially preferred). Particular preference is given to the couplers examples 3, 8, 34 listed by way of example).

As the silver halide used in the present invention, silver chloride, silver bromide, silver chlorobromide, silver iodochlorobromide, silver iodobromide, etc. can be used. It is preferable to use a silver chlorobromide or silver chloride emulsion which does not substantially contain silver iodide and has a silver chloride content of 90 mol % or more, more 95% or more, particularly 98% or more.

Further, in the photosensitive material according to the present invention, for the purpose of improving image sharpness, etc., the hydrophilic colloid layer is coated with European Patent No. 27-
Adding dyes (especially oxonol dyes) that can be decolorized by processing as described on page 76 so that the optical reflection density at 680 nm of the light-sensitive material is 0.70 or more,
It is preferred that the water-resistant resin layer of the support contains 12% by weight or more (more preferably 14% by weight or more) of titanium oxide that has been surface-treated with a di- to tetrahydric alcohol (for example, trimethylolethane).

Further, in the light-sensitive material according to the present invention, it is preferable to use a color image preservation improving compound as described in European Patent EP 0,277,589A2 together with a coupler. Particularly preferred is the combination with a pyrazoloazole coupler.

That is, the compound (F) and/or which chemically bonds with the aromatic amine developing agent remaining after color development processing to produce a chemically inert and substantially colorless compound.
Alternatively, a compound (G) that chemically bonds with the oxidized aromatic amine color developing agent remaining after color development processing to produce a chemically inert and substantially colorless compound is used simultaneously or singly. However, this is preferable in order to prevent the generation of stains and other side effects due to the reaction of the coupler with the color developing agent or its oxidized product remaining in the film during storage after processing.

[0052] The photosensitive material according to the present invention is also treated with anti-mildew agents as described in JP-A No. 63-271247 in order to prevent various types of mold and bacteria that grow in the hydrophilic colloid layer and degrade images. It is preferable to add an agent.

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

The photosensitive material according to the present invention may be exposed to visible light or infrared light. The exposure method may be low-intensity exposure or high-intensity short-time exposure, and particularly in the latter case, a laser scanning exposure method in which the exposure time per pixel is shorter than 10 -4 seconds is preferred. Further, during exposure, it is preferable to use a band stop filter as described in US Pat. No. 4,880,726. This eliminates optical color mixture and significantly improves color reproducibility.

[0055]

[Examples] The present invention will be explained in detail below with reference to Examples, but the present invention is not limited thereto.

Example 1 After corona discharge treatment was applied to the surface of a paper support laminated on both sides with polyethylene, a gelatin undercoat layer containing sodium dodecylbenzenesulfonate was applied, and various photographic constituent layers were further coated. Multilayer color photographic paper A having the layer structure shown below was produced. The coating solution was prepared as follows.

Preparation of fifth layer coating solution 32.0 g of cyan coupler (ExC), color image stabilizer (C
pd-2) 3.0g, color image stabilizer (Cpd-4) 2.0
g, color image stabilizer (Cpd-6) 18.0 g, color image stabilizer (Cpd-7) 40.0 g, and color image stabilizer (Cpd-
8) To 5.0g, add 50.0cc of ethyl acetate and solvent (
Solv-6) 14.0g was added and dissolved, and this solution was mixed with 20g of sodium dodecylbenzenesulfonate containing 8cc.
% gelatin aqueous solution and then emulsified and dispersed using an ultrasonic homogenizer to prepare an emulsified dispersion. On the other hand, silver chlorobromide emulsion (cubic, average grain size 0.58
A 1:4 mixture (Ag molar ratio) of a large size emulsion of μm and a small size emulsion of 0.45 μm. The coefficient of variation of grain size distribution is 0.09 and 0.11, respectively, and each size emulsion is A.
A particle containing 0.6 mol % of gBr locally on a part of the particle surface was prepared. This emulsion contains red-sensitive sensitizing dye E shown below at 0.9x per mole of silver for large size emulsions.
10-4 mol, or 1.1 x 1 for small size emulsions
0-4 mol is added. Further, chemical ripening of this emulsion was carried out by adding a sulfur sensitizer and a gold sensitizer. The above emulsified dispersion and this red-sensitive silver chlorobromide emulsion were mixed and dissolved to prepare a fifth layer coating solution having the composition shown below.

Coating solutions for the first to fourth, sixth and seventh layers were also prepared in the same manner as the fifth layer coating solution. As the gelatin hardening agent for each layer, 1-oxy-3,5-dichloro-s-triazine sodium salt was used. In addition, the total amount of Cpd-10 and Cpd-11 was 25% each in each layer.
．． It was added at a concentration of 0 mg/m2 and 50.0 mg/m2. The following spectral sensitizing dyes were used in the silver chlorobromide emulsion of each light-sensitive emulsion layer.

[Blue-sensitive emulsion layer] Sensitizing dye A

[0060]

[Chemical formula 1]

and sensitizing dye B

[0062]

[Case 2]

(2.0 x 10-4 mol each for large-sized emulsions and 2.5 x 10-4 mol each for small-sized emulsions per mol of silver halide) [green-sensitive emulsions] Layer] Sensitizing dye C

[0064]

[Chemical formula 3]

(per mole of silver halide, 4.0 x 10-4 mol for large size emulsions, 5.6 x 10-4 mol for small size emulsions) and sensitizing dye D

0
066]

[C4]

(7.0 x 10-5 mol for large size emulsions and 1.0 x 10-5 mol for small size emulsions per 1 mol of silver halide) [Red-sensitive emulsion layer] Increase Sensitive dye E

[0068]

[C5]

(0.9 x 10-4 mol for large size emulsions and 1.1 x 10-4 mol for small size emulsions per 1 mol of silver halide) Furthermore, the following compound is added to the halogen 2.6×10 −3 mol was added per mol of silveride.

[0070]

[C6]

Further, for the blue-sensitive emulsion layer, the green-sensitive emulsion layer and the red-sensitive emulsion layer, 1-(5-methylureidophenyl)-5-mercaptotetrazole was added to each mole of silver halide at 8.5×10 − 5 moles, 7.7 x 10-
4 moles, 2.5 x 10-4 moles were added. In addition, 4-hydroxy-6-
Methyl-1,3,3a,7-tetrazaindene at 1×10 −4 mol and 2× mol per mol of silver halide, respectively.
10-4 mol was added. In addition, in order to prevent irradiation, the following dyes are added to the emulsion layer (the amount in parentheses indicates the coating amount).
was added.

[0072]

[C7]

(Layer structure) The composition of each layer is shown below. The numbers represent the coating amount (g/m2). The silver halide emulsion represents the coated amount in terms of silver.

Support polyethylene laminate paper [The polyethylene on the first layer side contains a white pigment (TiO2) and a bluish dye (ulmarine)]

0
075] First layer (blue-sensitive emulsion layer)

Second layer (color mixing prevention layer)

Third layer (green-sensitive emulsion layer)

Fourth layer (ultraviolet absorbing layer)

Fifth layer (red-sensitive emulsion layer)

[0080] Sixth layer (ultraviolet absorbing layer)

Seventh layer (protective layer)

[0082]

[Chemical formula 8]

[0083]

[Chemical formula 9]

[0084]

[Chemical formula 10]

[0085]

[Chemical formula 11]

[0086]

[Chemical formula 12]

[0087]

[Chemical formula 13]

[0088]

[Chemical formula 14]

[0089]

[Chemical formula 15]

[0090]

[Chemical formula 16]

First, each sample was subjected to gradation exposure using a sensitometric filter using a sensitometer (manufactured by Fuji Photo Film Co., Ltd., FWH type, light source color temperature 3200°K). The exposure at this time was carried out so that the exposure time was 0.1 seconds and the exposure amount was 250 CMS.

[0092] The above photosensitive material can also be used in an automatic printer F.
Imagewise exposure was carried out using AP3500 (manufactured by Fuji Film Corporation), and continuous processing (running test) was carried out using the following processing steps and processing solution until twice the bleach-fix solution was replenished. However, the following three types of replenishment methods were used for the bleach-fixing replenisher.

[0093] The composition of each treatment solution is as follows.

[0094]

[0095]

[Bleach-fixing replenisher ■]

[Bleach-fixing replenisher (■)] The above bleach-fixing replenisher (■) was replenished in an amount of 30 ml per 1 m 2 of the light-sensitive material.

[Bleach-fix replenisher ■] 3 of A, B, and C below
Divide into two parts, each per 1m2 of photosensitive material.
8ml, 17ml and 5ml (total 30ml) were refilled directly into the tank. Part A

0099 Part B

0100 Part C

[Rinse liquid] (tank liquid and refill liquid are the same)
Ion exchange water (calcium, magnesium 3pp each)
m or less)

A running test was carried out using each of the above three types of bleach-fixing replenisher, and the above-mentioned sensitometry was performed in the running state. In the processed sensitometry, in order to confirm the desilvering performance, the amount of residual silver was measured using fluorescent X-rays at the maximum density part. In addition, in order to confirm the white background, the minimum density of yellow in the unexposed area was measured using a Macbeth densitometer.

Furthermore, the amount of overflow of the bleach-fix solution during each running test was measured, and 1 m2 of the photosensitive material was measured.
The liquid volume per unit was calculated. The results are shown in Table 6.

[0104]

[Table 6]

From the results shown in Table 6, according to the present invention, the amount of waste liquid was significantly reduced, and satisfactory results were obtained without impairing desilvering properties or photographic properties.

Example 2 Photographic papers B, C, and D were prepared in the same manner as multilayer color photographic paper A in Example 1, except that the silver chloride content in the emulsion composition of each layer was changed as shown in Table 7. did.

[0107]

[Table 7]

[0108] Photographic papers A, B, and
C and D were subjected to sensitometry in the same manner as in Example 1, treated with bleach-fix replenisher (1) and running solution (2), and the residual silver amount and minimum density were measured in the same manner as in Example 1. The results are shown in Table 8.

[0109]

[Table 8]

According to the present invention, if a high silver chloride emulsion containing 90 mol % or more of chloride ions of photographic papers A, B, and C is used, the effects of the present invention can be significantly obtained.

Claims (3)

[Claims] Claim 1: In a continuous processing step in which a silver halide color photographic light-sensitive material is exposed and then subjected to color development, bleach-fixing, and water washing or stabilization treatment, two or more types of bleach-fix replenishers are used in a concentrated solution part. A method for processing a silver halide color photographic light-sensitive material, characterized in that each concentrate is directly replenished into a bleach-fixing tank without being mixed for each unit processing amount of the light-sensitive material. 2. The silver halide color photographic light-sensitive material according to claim 1, wherein the bleach-fix replenisher comprises three concentrated liquid parts each containing a bleach, a fixing agent, and an acid as main components. processing method. 3. The silver halide color photographic material according to claim 2, wherein the silver halide color photographic material contains a high silver chloride emulsion containing 90 mol % or more of chloride ions in at least one layer. How to process