JP2007101680A - Additive agent for washing-alternative stabilizing solution - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a washing-alternative stabilizing solution which prevents wet heat cyan fading and improves image preservability, when a processed photosensitive material is stored over a long period of time in a high-humidity or high-temperature environment, and which prevents adhesion of processing solution components to a squeeze roller in a stabilizing solution tank, roller contamination and occurrence of a dent on a photosensitive material surface. <P>SOLUTION: A processing composition is added as an additive agent to a washing-alternative stabilizing solution and/or a wash-alternative stabilizing replenisher solution, containing an alkali metal sulfite for processing a silver halide color photographic sensitive material, wherein the processing composition contains ammonium sulfate. In particular, the content of the ammonium sulfate is 1.0-5.0 mol/l. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a photographic development processing composition for a silver halide photographic light-sensitive material (hereinafter sometimes simply referred to as a light-sensitive material), and in particular, in addition to a washing solution and a processing solution, The present invention relates to an additive agent for improving the treatment performance of a bath.

  In recent years, automatic development processing machines called minilabs that are installed at the photographic store front and process photographic photosensitive materials have become widespread for quick service to general users and rationalization of collection and delivery between photographic stores and processing shops. . In minilab development processing, it is advantageous from the standpoint of process simplicity and quality constancy that the processing chemicals to be used are pre-prepared and are in the form of a prepared processing agent that can be used as it is or simply by diluting with water. Yes, it is widely used. The blending processing agent is composed of a color development processing agent, a processing agent having bleaching ability and a processing agent having fixing ability (or a bleach-fixing processing agent having both functions), a processing agent for washing substitute stabilizer. The preparation treatment is in the form of a liquid composition in which the constituent chemicals are preliminarily dissolved in a solvent such as water, and in the form of a liquid concentrate composition that can be used to prepare a treatment liquid by simple preparation operations such as mixing and dilution with water. In addition, there is a form of a solid processing agent in which the processing agent component is mixed as a solidified product such as powder, granule, tablet, etc., and it is generally supplied in a preferable form according to the actual situation of a developing laboratory (minilab). It is.

  Each preparation processing agent such as a color development processing agent, a processing agent having bleaching ability and a processing agent having fixing ability (or a bleach-fixing processing agent having both functions), and a processing agent for alternative washing solution for water washing is suitable for rapid processing. Improvements are being sought and developed to meet the required characteristics such as stain deterrence, image quality maintenance such as saturation and gradation, and environmental safety suitability. The washing-replacement stabilizer is a washing-replacement action that does not drain water instead of washing, in which the processing solution components occluded in the processed photosensitive material are washed out from the photosensitive material at the final stage of the processing step, and the processed photosensitive material. Since it has the role of simultaneously performing the generation of stains during storage over time and the stabilizing action to prevent image discoloration, using this, the conventional water washing process and the stabilizing liquid process are performed simultaneously, and the discharge The amount of water can be greatly reduced or eliminated (for example, see Patent Document 1).

Japanese Patent Laid-Open No. 62-246055

  However, the water-washing stable bath has advantages such as reduced water costs, chemical costs, and reduced heat-up costs, but is easily affected by the pH of the previous process and has been treated with residual sensitizing dye and residual silver salt. The photosensitive material is stained over time, and the stability of the image is insufficient due to pH fluctuations in the stable bath. In particular, yellow stain increases over time after processing, and the processing solution is added to the squeeze roller in the stabilizing bath. Ingredients and their decomposition products (sulfides, etc.) are attached and crystallized, which is accompanied by adverse effects such as roller dirt and photosensitive material surface being easily scratched. Is required.

In the above-mentioned Patent Document 1, it is described that the occurrence of stain is suppressed by adjusting the pH of the image stabilizer to a specified range, and that the image storage stability is improved and the processing time can be shortened by adding an ammonium salt. In reality, however, further improvements are required.
On the other hand, when sulfite is contained in the stabilizing solution, sulfidation is prevented and the occurrence of roller dirt and scratches on the photosensitive material surface is reduced, and the problems related to maintenance are reduced. It has been found that the deterioration of cyan amber color (referred to as wet heat cyan amber color) increases and the image quality, particularly when posted, is impaired.

Despite the efforts to improve the problems as described above, there is still a need for means for rinsing alternative stabilizers that can ensure both the image quality of the processed photosensitive material and the stable operation of the minilab.
An object of the present invention is to solve the above-described problems. Specifically, it is possible to improve image storability by preventing wet heat cyan fading when the processed photosensitive material is aged at high humidity or high temperature. It is an object of the present invention to provide an alternative stabilization means for washing that can be applied to a squeeze roller of a stabilizing solution tank and can prevent roller contamination due to adhesion and crystallization of a processing solution component and pressing of the surface of a photosensitive material.

  In the course of diligently studying the above object, the present inventor, when sulfite and ammonium sulfate are contained in the stabilizer, suppresses wet heat cyan discoloration caused by sulfite, and also prevents sulfurization of sulfite and roller dirt. We found an unexpected effect that the effect is maintained. The present invention has been made based on this discovery, and has the following configuration.

1. A processing composition to be added as an additive to an alkali metal sulfite-containing water-washing alternative stabilizer and / or water-washing alternative stable replenisher for processing silver halide color photographic light-sensitive materials, characterized by containing ammonium sulfate Alternative additive for stabilizers.
2. 2. Additive agent for washing substitute stabilizer according to 1 above, wherein the content of ammonium sulfate is 1.0 to 5.0 mol / L.
3. Furthermore, the additive for washing | cleaning alternative stabilizers of said 1 or 2 characterized by containing 20-200 mg / L of 1, 2- benzothiazolin-3-one.
4). Halogenation characterized by adding an additive agent as described in any one of 1 to 3 above to a water-washing alternative stabilizer and / or a water-washing alternative replenisher containing an alkali metal sulfite salt for processing silver halide color photographic light-sensitive materials Processing method of silver color photographic light-sensitive material.
5. 5. The method for processing a silver halide color photographic light-sensitive material as described in 4 above, wherein the concentration of ammonium sulfate in the water-washing alternative stabilizing solution and / or the water-washing alternative stable replenisher is 1.0 to 10.0 mmol / L. .

  The ammonium sulfate-containing additive according to the present invention, which is added to a water-washing alternative stabilizer and / or a water-washing alternative stable replenisher containing an alkali metal sulfite, suppresses wet heat cyan fading, and also sulphites in the stabilizer bath Sulfuration prevention, squeeze roller crystals adhering to the surface of the photosensitive material, and damage to the photosensitive material surface are also prevented, and problems associated with image quality and processing equipment maintenance associated with the use of a washing-replacement stabilizer are solved.

  The first feature of the present invention is that an additive is used for an alternative stabilizer for washing with water containing alkali metal sulfite. Additives are stable by compensating for the components that have fluctuated excessively in the processing solution composition during continuous development processing, or when the processing solution components have deteriorated during long periods of operation suspension. Therefore, as a general concept, additive is a processing agent that is used as an auxiliary agent for developers, bleaching solutions, fixing solutions, bleach-fixing solutions, etc. In the past, it was unthinkable to use additive as a water-washing alternative stabilizing solution, which is a dilute aqueous solution for conditioning purposes at the final stage after completion of both the development process and the desilvering process. And in this invention, when it uses for the washing | cleaning alternative stability liquid and the water washing alternative stable replenishment liquid, the said remarkable effect was discovered.

  The second feature of the present invention is that it is an ammonium sulfate-containing additive intended for an alternative washing solution containing an alkali metal sulfite. That is, by using this additive, the water-washing alternative stabilizer is the coexistence of alkali metal sulfite and ammonium sulfate. As described above, the alkali metal sulfite has a defect that the wet heat cyan discoloration is deteriorated despite the effect of suppressing the generation of scratches on the surface of the photosensitive material, such as sulfidation and roller dirt, When ammonium sulfate coexists, this defect disappears unexpectedly, and further, the function of suppressing sulfidation, roller contamination, and scratches on the photosensitive material surface is maintained, and the image storability improving effect of ammonium sulfate is also maintained.

Japanese Patent Application Laid-Open No. 52-246055 describes an aqueous washing substitute stabilizer containing an ammonium salt, but differs from the aqueous washing substitute stabilizer used in the present invention in that it does not contain an alkali metal sulfite. Thus, the problems to be solved by the present invention and the effects of the invention are also different. .
Japanese Patent Application Laid-Open No. 61-118753 describes a water-washing alternative stabilizer containing a sulfite, in order to prevent deterioration of the image of a light-sensitive material using a specific yellow coupler over time. This is different from the washing-substituting stabilizer used in the present invention, and the problems to be solved by the present invention and the effects of the invention are also different.
As long as it is an additive containing ammonium sulfate, the additive for a washing-washing alternative stabilizing solution of the present invention may be either liquid or solid (powder, tablet, granule), or may be a liquid or solid of ammonium sulfate single component. Alternatively, it may be a solution or a mixture in which ammonium sulfate is the main component and other components coexist.

As a form of use, either a form directly added to the water washing alternative stable bath or a form added to the water washing alternative stable replenisher may be used. Further, in the present invention, the additive agent is added as an additional auxiliary component to the water washing alternative stable bath or the water washing alternative stable replenishment liquid storage tank as needed when the image quality deterioration or roller dirt is likely to occur by the water washing alternative stable bath step. The normal use form is used in the form, but the present invention can also be applied to a form added as a standard component of the washing substitute stable solution or the washing substitute stable replenisher.
When the additive is a liquid, the content of ammonium sulfate is 1.0 to 5.0 mol / L, preferably 1.1 to 4.0 mol / L, more preferably 1.2 to 3.0 mol / L. L. By using the additive agent within this range, the ammonium sulfate concentration in the washing substitute stabilizer and the washing substitute stable replenisher is maintained at an appropriate concentration to exhibit its function.

Moreover, it is preferable that the additive agent of a liquid agent contains an antibacterial and antifungal agent in addition to ammonium sulfate. As the antibacterial and antifungal agent, 1,2-benzothiazoline-3-one is preferable, and its preferable concentration is 20 to 200 mg / L, more preferably 30 to 180 mg / L. By including 1,2-benzothiazolin-3-one, the growth of water-repellent microorganisms and bacteria in the washing-replacement stabilizer and washing-replacement stability replenisher is suppressed, and the processing quality is maintained and the processor is managed smoothly. The stable operation of the laboratory is performed.
The water-washing alternative stabilizing liquid and / or water-washing alternative stable replenisher according to the present invention contains an alkali metal sulfite salt, and sulfuration, roller contamination, and generation of scratches on the photosensitive material surface are suppressed. The content of the alkali metal sulfite is preferably 4 mmol / L or more and 100 mmol / L or less. If the concentration is lower than this range, the effect of containing an alkali metal sulfite is poor, and if it is higher than this range, the original action and effect of the water-washing alternative stable station are poor.

  The additive agent may be a single agent of ammonium sulfate, or may be a single agent mixture of ammonium sulfate and 1,2-benzothiazolin-3-one or a non-mixed two agent composition. Furthermore, in addition to these, it may contain constituents of a washing-substituting stabilizer and a binder (for tableting and granulating purposes) described later.

The pH of the water-washing alternative stable solution and / or the water-washing alternative stable replenisher is preferably 2 to 10, more preferably 4 to 8. Since the pH buffer capacity of the stabilizer is generally low, this range is also appropriate for the pH of the additive of the present invention. When the pH is lower than this, the desilvering property is improved, but the deterioration of the solution and the leuco conversion of the cyan dye are promoted. On the contrary, if the pH is higher than this, desilvering is delayed and stain is likely to occur.
To adjust the pH, alkali potassium hydroxide, sodium hydroxide, lithium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, etc., or acids such as sulfuric acid, hydrochloric acid, nitric acid, acetic acid, citric acid, etc. An acidic or alkaline buffering agent or the like (the buffering agent described in the section of the developer composition described later can be used) can be added.
Moreover, 1.05-1.40 are preferable and, as for the specific gravity of the additive agent of this invention, 1.10-1.30 are still more preferable.
The additive agent of the present invention is added to the washing substitute stabilizer and / or the washing substitute stable replenisher. The addition amount is preferably 1 to 100 ml, more preferably 3 to 50 ml, per liter of the water-washing alternative stable solution and / or water-washing alternative stable replenisher.

The additive may further contain constituent components of a water-washing alternative stabilizing solution and a water-washing alternative stable replenisher described later.
The additive agent of the present invention can be stored in a general photographic processing solution storage container. A preferable storage unit is 10 to 2000 ml / piece, more preferably 20 to 1000 ml / piece.
An example of a preferred container used in a typical storage configuration is a polyethylene bottle. For polyethylene bottles, a container made of high density polyethylene (hereinafter referred to as HDPE) having a density of 0.941 to 0.969 and a melt index of 0.3 to 5.0 g / 10 min as a single constituent resin. It is. A more preferable density is 0.951 to 0.969, and still more preferably 0.955 to 0.965. Moreover, a more preferable melt index is 0.3-5.0, More preferably, it is 0.3-4.0. The melt index is a value measured under a load of 2.16 kg at a temperature of 190 ° C. according to the method defined in ASTM D1238. The container is preferably 500-1500 μm thick. However, the processing agent container used in the present invention is not limited to the HDPE container that is convenient for mounting on a developing machine, and other HDPE such as polyethylene terephthalate (PET), polyvinyl chloride (PVC), and low density polyethylene (LDPE). Other than conventional container materials, and even HDPE, containers made from materials other than the above ranges of density and melt index can be used.

Another preferred form of the container for the concentration treatment agent of the present invention is a container made of flexible paper or plastic film, and a typical example thereof is a gusset pouch-type film container.
The gusset pouch-type film container has a columnar body, and the opposite inner surface of the lower end of the columnar part is bonded and sealed to form a container bottom, and the opposite inner surface of the upper end of the columnar part is peeled off and sealed. It consists of a seal portion, and the treatment agent stored by opening the seal portion after being peeled off can be discharged.
The sealing method is not particularly limited as long as it does not interfere with opening and storage, and any known sealing agent can be used, and either a heat sealing method or a solvent or diluted adhesive method may be used.
The material of the constituent material of the gusset pouch-type film container is water vapor barrier paper, plastic, laminated paper, plastic / paper laminated material, metal foil / plastic laminated material, film obtained by depositing aluminum, glass or silica on a PET substrate, A material that can form a wrapping material having a columnar body and is flexible is selected from sheets of these composite materials. Examples of preferred materials include PE / paper / PE / Al foil / PET / PE / PEF composite, PE / paper / PE / Al foil / PET / PE composite, PE / paper / PE / Al Examples include a composite material having a foil / PE configuration.

Yet another preferred form of the container for a concentration treatment agent made of flexible paper or plastic film may be a gable top type container that is also used for milk packs and sake packs. In this type of container, preferred materials are the above-mentioned laminated materials and water-resistant processed paper.
In addition, a form accommodated in a so-called cubitener inserted into a reinforcing cardboard in accordance with its inner method is also preferable.

These types of containers are preferably made of materials each having a water vapor permeability of 200 mL / m ² · 24 hrs · Pa or less. The oxygen permeability coefficient "O ₂ permeation of plastic Conti toner, Modern Packing _{(O 2 permeation of plastic container,} Modern Packing; NJ Calyan, 1968) measured by the method described in December pages 143 to 145 of As the high-barrier packaging material, those described in the new development of functional packaging materials (Toray Research Center, February 1990) can be used.
In addition, low oxygen-permeable and low water vapor-permeable containers disclosed in JP-A-63-17453, and vacuum packaging materials disclosed in JP-A-4-19655 and JP-A-4-230748 are also preferable container material references. Can be cited.
Next, the water-washing alternative stabilizer and / or the water-washing alternative stabilizer to which the additive of the present invention is added will be described. As described above, the additive may contain the components shown individually.

  Further, the water washing substitute stabilizing solution, the water washing substitute stable replenisher, the additive, or both of them can contain various other fluorescent brighteners, antifoaming agents, surfactants, polyvinylpyrrolidone and the like.

  The water-washing alternative stabilizing solution and water-washing alternative replenisher to which the present invention is applied are water-soluble salts of ethylenediaminetetraacetic acid, water-soluble salts of nitrilotriacetic acid, water-soluble polyphosphates, and other 3 of JP-A 61-42660. The metal repairing agent described on pages 6 to 6 and the compounds for reducing calcium and magnesium described in JP-A-62-288838 can be used effectively. Further, chlorinated fungicides such as isothiazolone compounds and siabendazoles described in JP-A-57-8542, chlorinated sodium isocyanurate described in JP-A-61-120145, JP-A-61-267761 Benzotriazole described in Japanese Laid-open Patent Publication No. 61, thiazolylbenzimidazoles and alkylguanidines described on page 6 of Japanese Patent Laid-Open No. 61-42660, copper ions, and others, "History of Antibacterial and Antifungal" by Hiroshi Horiguchi (1986) ) Sankyo Publishing, Sanitary Technology Association, edited by “Microbial Decontamination, Sterilization, and Antifungal Technology” (1982) Industrial Technology Association, Japanese Society for Antibacterial and Antifungal Studies, “Encyclopedia of Antibacterial and Antifungal Agents” (1986) It is also possible to use a bactericidal agent. Further, in the case of a solid agent, a known binder (binder) such as PVA, polyacrylic acid or polymethacrylic acid can be used for molding.

  Further, aldehydes such as formaldehyde, acetaldehyde, and pyrubinaldehyde that inactivate the remaining magenta coupler to prevent dye fading and stain formation, methylol compounds and hexamethylenetetramine described in US Pat. No. 4,786,583, Hexahydrotriazines described in U.S. Pat. No. 153348, formaldehyde bisulfite adducts described in U.S. Pat. No. 4,921,779, azolylmethylamines described in Seized Patent Publication Nos. 504609, 519190, etc. Also good. Furthermore, a surfactant can be used as a draining agent, and a chelating agent represented by EDTA can be used as a water softening agent.

[Color development process]
Next, a color development process using the additive agent of the present invention will be described.
The color development process to which the present invention is applied consists of a color development process, a desilvering process, a washing or stabilizing bath process and a drying process, and each process includes auxiliary processes such as a rinsing process, an intermediate washing process, and a neutralization process. A process can also be inserted. The desilvering process is performed by a one-step process using a bleach-fixing solution, but may be a separate desilvering process including a bleaching process and a fixing process. In addition to the water-washing alternative stable bath, an image stabilizing bath for the purpose of image stabilization can be provided between the water-washing alternative stable bath step and the drying step.

Here, the color development time (that is, the time during which the color development process is performed) is preferably 45 seconds or less, more preferably 30 seconds or less, still more preferably 28 seconds or less, particularly preferably 25 seconds or less and 6 seconds or more, and most preferably 20 seconds. 6 seconds or less. Similarly, the bleach-fixing time (that is, the time for performing the bleach-fixing step) is preferably 45 seconds or less, more preferably 30 seconds or less, further preferably 25 seconds or less and 6 seconds or more, particularly preferably 20 seconds or less and 6 seconds or more. It is. Moreover, the rinse (water-washing alternative stable bath) time (namely, water-washing alternative stable bath time) is preferably 90 seconds or shorter, more preferably 30 seconds or shorter, and even more preferably 30 seconds or shorter and 6 seconds or longer.
In the processing steps and processing operations, as in the above example, the washing alternative stability step (liquid) is often referred to as a rinsing step (liquid). Therefore, also in this specification, in the description of the steps and work surfaces, “Washing alternative stability process (liquid)” may be referred to as “rinsing process (liquid)”.

  The color development time refers to the time from when the photosensitive material enters the color developer until it enters the bleach-fixing solution in the next processing step. For example, when processed by an automatic developing machine, the time during which the photosensitive material is immersed in a color developer (so-called submerged time) and the photosensitive material leaves the color developer and is bleached and fixed in the next processing step. The sum of both the time during which air is conveyed toward the liquid (so-called air time) and the color development time. Similarly, the bleach-fixing time refers to the time from when the photosensitive material enters the bleach-fixing solution until the next washing or stabilizing bath. The rinse (washing substitute stabilization) time refers to the time (so-called liquid time) that the photosensitive material is in the solution for the drying process after entering the rinse solution (washing substitute stabilization solution).

  The processing solution temperature in the color development step, the bleach-fixing step, and the rinsing step is generally 30 to 40 ° C., but is preferably 38 to 60 ° C., more preferably 40 to 50 ° C. for rapid processing.

The amount of rinsing solution can be set in a wide range depending on the characteristics of the photosensitive material (for example, depending on the material used such as coupler) and application, the temperature of the rinsing solution (washing water), the number of rinsing solutions (washing tank) (stage number), and various other conditions Can do. Of these, the relationship between the number of rinsing liquid tanks (flush tanks) and the amount of water in the multi-stage counter-current system is the Journal of the Society of Motion Picture and Motion of Picture Picture and Television Engineers) Vol. 64, p. It can be determined by the method described in 248-253 (May 1955).
Usually, the number of stages in the multistage countercurrent system is preferably from 3 to 15, particularly preferably from 3 to 10.

  According to the multi-stage counter-current system, the amount of the rinse liquid can be greatly reduced, and the increase of the residence time of water in the tank causes problems such as bacteria breeding and the generated suspended matter adhering to the photosensitive material. As a solution, a rinsing solution containing an antibacterial and antifungal agent described later is preferable.

  The developed silver halide color photographic material is subjected to post-processing such as a drying step. In the drying process, drying is performed by absorbing moisture with a squeeze roller or cloth immediately after the development process (rinsing process) from the viewpoint of reducing the amount of moisture carried into the image film of the silver halide color photographic light-sensitive material. It is also possible to expedite. Of course, drying can be accelerated by increasing the temperature or changing the shape of the spray nozzle to increase the drying air. Further, as described in JP-A-3-157650, drying can be accelerated by adjusting the blowing angle of the dry air to the photosensitive material or by the method of removing the exhaust air.

The components of the treatment liquid used for the treatment of the color treatment and the treatment liquid other than the above-described stable washing bath alternative process will be described.
In this specification, unless there is a special meaning which distinguishes a tank liquid and a replenisher, both are expressed as a use liquid collectively.

The color developer contains a color developing agent.
Preferred examples of the color developing agent include known aromatic primary amine color developing agents, particularly p-phenylenediamine derivatives. Representative examples are shown below, but are not limited thereto.

1) N, N-diethyl-p-phenylenediamine 2) 4-amino-3-methyl-N, N-diethylaniline 3) 4-amino-N- (β-hydroxyethyl) -N-methylaniline 4) 4- Amino-N-ethyl-N- (β-hydroxyethyl) aniline 5) 4-Amino-3-methyl-N-ethyl-N- (β-hydroxyethyl) aniline 6) 4-Amino-3-methyl-N- Ethyl-N- (3-hydroxypropyl) aniline 7) 4-Amino-3-methyl-N-ethyl-N- (4-hydroxybutyl) aniline 8) 4-Amino-3-methyl-N-ethyl-N- (Β-Methanesulfonamidoethylaniline 9) 4-amino-N, N-diethyl-3- (β-hydroxyethyl) aniline 10) 4-amino-3-methyl-N-ethyl-N- (β-meth Ciethyl) aniline 11) 4-amino-3-methyl-N- (β-ethoxyethyl) -N-ethylaniline 12) 4-amino-3-methyl-N- (3-carbamoylpropyl-Nn-propyl- Aniline 13) 4-Amino-N- (4-carbamoylbutyl-Nn-propyl-3-methylaniline 15) N- (4-Amino-3-methylphenyl) -3-hydroxypyrrolidine 16) N- (4 -Amino-3-methylphenyl) -3- (hydroxymethyl) pyrrolidine 17) N- (4-amino-3-methylphenyl) -3-pyrrolidinecarboxamide

Of the above p-phenylenediamine derivatives, exemplary compounds 5), 6), 7), 8) and 12) are particularly preferred, and among them, compounds 5) and 8) are preferred. Moreover, these p-phenylenediamine derivatives are usually in the form of a salt such as sulfate, hydrochloride, sulfite, naphthalene disulfonate, p-toluenesulfonate in the state of a solid material.
The content of the aromatic primary amine developing agent in the processing solution is such that the concentration of the developing agent in the working solution is 2 to 200 mmol, preferably 6 to 100 mmol, more preferably 10 mmol to 1 L of the developing solution. It is added to 40 mmol.

The color developer may contain a small amount of sulfite ions or may be substantially free of sulfite ions depending on the type of the light-sensitive material, but in the present invention, it is preferable to contain a small amount of sulfite ions. While sulfite ions have a significant preserving action, excessive amounts may have an undesirable effect on photographic performance during color development.
Moreover, you may contain a small amount of hydroxylamine. If hydroxylamine (usually used in the form of hydrochloride or sulfate, but omits the salt form below), it acts as a preservative for the developer as well as sulfite ion, but at the same time it contains hydroxylamine itself. Since the silver developing activity may affect the photographic characteristics, it is necessary to keep this addition amount small.

  In addition to the hydroxylamine and sulfite ions, an organic preservative may be added to the color developer as a preservative. The organic preservative refers to all organic compounds that reduce the deterioration rate of the aromatic primary amine color developing agent by being contained in the processing solution of the photosensitive material. That is, it is an organic compound having a function of preventing air oxidation of color developing agents, among others, the above hydroxylamine derivatives, hydroxamic acids, hydrazides, phenols, α-hydroxy ketones, α-amino ketones. Saccharides, saccharides, monoamines, diamines, polyamines, quaternary ammonium salts, nitroxy radicals, alcohols, oximes, diamide compounds, and condensed amines are particularly effective organic preservatives. These are disclosed in JP-A 63-4235, 63-30845, 63-21647, 63-44655, 63-53551, 63-43140, 63-56654, 63- 58346, 63-43138, 63-146041, 63-44657, 63-44656, U.S. Pat.Nos. 3,615,503, 2,494,903, JP-A-52-143020, JP-B-48-30496 It is disclosed in each gazette or specification such as No ..

Other preservatives include various metals described in JP-A-57-44148 and 57-53749, salicylic acids described in JP-A-59-180588, and JP-A-54-3532. The alkanolamines described herein, polyethyleneimines described in JP-A-56-94349, aromatic polyhydroxy compounds described in US Pat. No. 3,746,544, and the like may be contained as necessary. In particular, alkanolamines such as triethanolamine and triisopropanolamine, substituted or unsubstituted dialkylhydroxylamines such as disulfoethylhydroxylamine, diethylhydroxylamine, or aromatic polyhydroxy compounds may be added. .
Among the organic preservatives, details of the hydroxylamine derivative are described in JP-A Nos. 1-97953, 1-186939, 1-186940, 1-187557 and the like. In particular, adding both a hydroxylamine derivative and amines may be effective in improving the stability of the color developer and improving the stability during continuous processing.
Examples of the amines include cyclic amines as described in JP-A-63-239447, amines as described in JP-A-63-128340, and other JP-A-1-86939. Examples thereof include amines described in JP-A-1-187557. Although the content of the preservative in the processing agent varies depending on the type of the preservative, it is generally added so that the concentration in the working solution is 1 to 200 mmol, preferably 10 to 100 mmol, per liter of the developing solution. It is done.

To the color developer, for example, a developer for color paper may contain chlorine ions as necessary. Color developers (especially developers for color print materials) usually contain chlorine ions of 3.5 × 10 ^{−2 to} 1.5 × 10 ⁻¹ mol / L, but chlorine ions are usually a by-product of development. In many cases, it is unnecessary to add to the replenishing developer. The developer for the photosensitive material for photographing does not have to contain chlorine ions.

It regard bromine ion, bromide ion in the color developing solution, 1～5X10 ^-3 mol / L approximately in the processing of photographic materials, also, in the processing of the print material is less 1.0 × 10 ^-3 mol / L Is preferred. However, color developers often do not need the same as the above-mentioned chlorine ions, but when added, bromine ions are added to the processing solution as necessary so that the bromine ion concentration falls within the above range. There is also.
When the photosensitive material to be obtained is obtained from a silver iodobromide emulsion such as a color negative film or a color reversal film, the situation is the same with respect to iodine ions, but usually iodine ions are released from the photosensitive material. In general, the iodine ion concentration is about 0.5 to 10 mg per liter of the developing solution, and therefore it is usually not included in the replenishing solution.

When halide is used as an additive component in a developer or developer replenisher, examples of the chloride ion supply material include sodium chloride, potassium chloride, ammonium chloride, lithium chloride, nickel chloride, magnesium chloride, manganese chloride and calcium chloride. Of these, sodium chloride and potassium chloride are preferred.
Examples of bromide supply materials include sodium bromide, potassium bromide, ammonium bromide, lithium bromide, calcium bromide, magnesium bromide, manganese bromide, nickel bromide, cerium bromide and thallium bromide. Of these, potassium bromide and sodium bromide are preferred.
Sodium iodide and potassium iodide are used as a substance for supplying iodine ions.

  In the present invention, the developer is preferably added so that the pH of the developer is 9.0 to 13.5 and the pH of the replenisher is 9.0 to 13.5. An alkali agent, a buffering agent and, if necessary, an acid agent can be included so that the pH value can be maintained.

  In order to maintain the pH when the treatment liquid is prepared, it is preferable to use various buffering agents. Examples of the buffer include carbonate, phosphate, borate, tetraborate, hydroxybenzoate, glycyl salt, N, N-dimethylglycine salt, leucine salt, norleucine salt, guanine salt, 3,4- Dihydroxyphenylalanine salt, alanine salt, aminobutyrate, 2-amino-2-methyl-1,3-propanediol salt, valine salt, proline salt, trishydroxyaminomethane salt, lysine salt and the like can be used. In particular, carbonate, phosphate, tetraborate, and hydroxybenzoate have excellent buffering ability in the high pH range of pH 9.0 or higher, and adverse effects on photographic performance even when added to color developers (fogging, etc.) It is particularly preferable to use these buffering agents.

Specific examples of these buffering agents include sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, disodium phosphate, dipotassium phosphate, sodium borate, boric acid. Potassium, sodium tetraborate (borax), potassium tetraborate, sodium o-hydroxybenzoate (sodium salicylate), potassium o-hydroxybenzoate, sodium 5-sulfo-2-hydroxybenzoate (sodium 5-sulfosalicylate) ), Potassium 5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate), and the like. However, the present invention is not limited to these compounds.
Since the buffer is not a component that is reacted and consumed, the concentration of the developer and the replenisher prepared from the processing agent is 0.01 to 2 mol, preferably 0.1 to 0.5 mol, per liter. Thus, the addition amount in the composition is determined.

Various chelating agents that are precipitation inhibitors for other color developer components such as calcium and magnesium, or color developer stability improvers can also be added to the color developer. For example, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, ethylenediaminetetraacetic acid, N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N, N ′, N′-tetramethylenesulfonic acid, transsiloxanediaminetetraacetic acid, 1 , 2-diaminopropanetetraacetic acid, glycol ether diamine tetraacetic acid, ethylenediamine orthohydroxyphenylacetic acid, ethylenediamine disuccinic acid (SS form), N- (2-carboxylateethyl) -L-aspartic acid, β-alanine diacetic acid, 2 -Phosphonobutane-1,2,4-tricarboxylic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, N, N'-bis (2-hydroxybenzyl) ethylenediamine-N, N'-diacetic acid, 1,2- And dihydroxybenzene-4,6-disulfonic acid It is.
These chelating agents may be used in combination of two or more as required.
The amount of these chelating agents may be an amount sufficient to sequester metal ions in the prepared color developer. For example, it is added so as to be about 0.1 to 10 g per liter.

  If necessary, an arbitrary development accelerator can be added to the color developer. As development accelerators, see JP-B-37-16088, JP-A-37-5987, JP-A-38-7826, JP-A-44-12380, JP-A-45-9019 and U.S. Pat.No. 3,813,247. Thioether compounds represented, p-phenylenediamine compounds represented in JP-A-52-49829 and JP-A-50-15554, JP-A-50-137726, JP-B 44-30074, JP-A-56- Quaternary ammonium salts represented in 156826 and 52-43429, etc., U.S. Pat.Nos. 2,494,903, 3,128,182, 4,230,796, 3,253,919, Japanese Patent Publication No. 41-11431, U.S. Pat. 2,596,926 and 3,582,346, etc.Amine compounds described in each publication or specification, JP-B-37-16088, JP-A-42-25201, U.S. Pat.No. 3,128,183, JP-B-41-11431, JP-A-42-23883 And U.S. Pat.No. 3,532,501, etc. The 3-pyrazolidones or imidazoles may be added as needed. The addition amount of the developer and the replenisher prepared from the processing agent is determined so as to be 0.001 to 0.2 mol, preferably 0.01 to 0.05 mol, per liter.

In addition to the halogen ions, an optional antifoggant can be added to the color developer as necessary. Examples of the organic antifoggant include benzotriazole, 6-nitrobenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chloro-benzotriazole, 2-thiazolyl-benzimidazole, 2 -Representative examples include nitrogen-containing heterocyclic compounds such as thiazolylmethyl-benzimidazole, indazole, hydroxyazaindolizine, and adenine.
Further, various surfactants such as alkyl sulfonic acid, aryl sulfonic acid, aliphatic carboxylic acid, and aromatic carboxylic acid may be added to the color developer as necessary. The addition amount of the developer and the replenisher prepared from the processing agent is determined so as to be 0.0001 to 0.2 mol, preferably 0.001 to 0.05 mol, per liter.

  In the color developer, an optical brightener can be used as necessary. As the optical brightener, a bis (triazinylamino) stilbene sulfonic acid compound is preferred. As the bis (triazinylamino) stilbene sulfonic acid compound, known or commercially available niaminostilbene-based brighteners can be used. As the known bis (triazinylamino) stilbene sulfonic acid compound, for example, compounds described in JP-A-6-329936, JP-A-7-140625, JP-A-10-14049 and the like are preferable. Commercially available compounds are described, for example, in “Dyeing Note” 9th edition (Colored dyeing), pages 165 to 168. Among the compounds described therein, Blankophor BSU liq. And Hakkol BRK include preferable.

The processing solution for the desilvering process such as bleaching solution, bleach-fixing solution and fixing solution will be described.
The processing solution for the desilvering step is composed of a bleaching agent, a fixing agent, and an auxiliary agent that smoothly exerts their functions.
The bleaching solution or the bleach-fixing solution contains an aminopolycarboxylic acid iron (III) complex salt, and the processing solution is stable without precipitation in the range where the concentration does not exceed 3.0 mol / L. If it is more than / L, process quickness and low replenishment are ensured. Preferably, it is designed to be 0.2 to 2 mol per liter of the preparation liquid.

  As the bleaching agent, other known bleaching agents can be used in addition to the iron (III) complex salt of aminopolycarboxylic acid. Examples of bleaching agents that can be used in combination include iron (III) complex salts of organic acids such as citric acid, tartaric acid, malic acid, persulfates, and hydrogen peroxide.

  A preferable iron (III) complex salt of aminopolycarboxylic acid is an iron (III) complex salt of aminopolycarboxylic acid exemplified below. That is, biodegradable ethylenediamine disuccinic acid (SS form), N- (2-carboxylateethyl) -L-aspartic acid, betaalanine diacetic acid, methyliminodiacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, 1 , 3-diaminopropanetetraacetic acid, propylenediaminetetraacetic acid, nitrilotriacetic acid, cyclohexanediaminetetraacetic acid, iminodiacetic acid, glycol etherdiaminetetraacetic acid. These compounds may be any of sodium, potassium, thylium or ammonium salts. Among these compounds, ethylenediamine disuccinic acid (SS form), N- (2-carboxylateethyl) -L-aspartic acid, β-alanine diacetic acid, ethylenediaminetetraacetic acid, 1,3-diaminopropanetetraacetic acid, methyliminodioxy Acetic acid is preferable because its iron (III) complex salt has good photographic properties. These iron (III) complex salts may be used in the form of complex salts, or ferric salts such as ferric sulfate, ferric chloride, ferric nitrate, ferric ammonium sulfate, ferric phosphate. And a chelating agent such as aminopolycarboxylic acid may be used to form an iron (III) complex salt in a solution. Further, the chelating agent is used in excess as compared with the formation of the iron (III) complex salt.

  In the bleaching solution, various known organic acids (for example, acetic acid, lactic acid, glycolic acid, succinic acid, maleic acid, malonic acid, citric acid, sulfosuccinic acid, citric acid, tartaric acid, glutaric acid, lactic acid, etc.), organic bases (For example, imidazole, dimethylimidazole, etc.) or the compounds represented by the general formula (Aa) described in JP-A-9-211819 including 2-picolinic acid and kojic acid. It is preferable to contain the compound represented by the general formula (Bb) described. The amount of these compounds added is determined so that the concentration of the prepared treatment liquid is preferably 0.05 to 3.0 mol, more preferably 0.2 to 1.0 mol per liter. The organic acid is preferably a monobasic acid or a dibasic acid, and is particularly preferably a dibasic acid in that it is excellent in preventing precipitation and has no bleaching delay.

  The bleach-fixing solution and the fixing agent constituting the fixing solution are known fixing chemicals, that is, thiosulfates such as sodium thiosulfate and ammonium thiosulfate, thiocyanates such as sodium thiocyanate and ammonium thiocyanate, ethylenebisthioglycolic acid, One or two or more kinds selected from thioether compounds such as 3,6-dithia-1,8-octanediol and water-soluble silver halide solubilizers such as thioureas can be mixed and contained. A special bleach-fixing solution comprising a combination of a fixing agent described in JP-A-55-155354 and a large amount of a halide such as potassium iodide can also be used. In the present invention, it is preferable to use thiosulfate, particularly ammonium thiosulfate. The concentration of the fixing agent is preferably designed to be 0.3 to 3 mol per liter of the prepared solution when the bleach-fixing solution is prepared, and more preferably in the range of 0.5 to 2.0 mol. Designed.

  For fixers, sulfites (eg, sodium sulfite, potassium sulfite, ammonium sulfite, etc.), bisulfites (eg, ammonium bisulfite, sodium bisulfite, potassium bisulfite, etc.), metabisulfite are used as preservatives. Contains sulfite ion-releasing compounds such as salts (eg, potassium metabisulfite, sodium metabisulfite, ammonium metabisulfite, etc.), arylsulfinic acid such as p-toluenesulfinic acid, m-carboxybenzenesulfinic acid, etc. It is preferable to do this. These compounds are preferably contained in an amount of about 0.02 to 1.0 mol / L (as the concentration of the prepared treatment liquid) in terms of sulfite ions or sulfinate ions.

  As a preservative, ascorbic acid, a carbonyl bisulfite adduct, a carbonyl compound, or the like may be added in addition to the above.

  The following description will be made including the components that may be contained in any of the bleaching solution, the fixing solution, and the bleach-fixing solution.

The pH range at the time of dissolution of the treatment solution is preferably from 3 to 8, and more preferably from 4 to 8. When the pH is lower than this, the desilvering property is improved, but the deterioration of the solution and the leuco conversion of the cyan dye are promoted. On the contrary, if the pH is higher than this, desilvering is delayed and stain is likely to occur.
In order to adjust the pH, potassium hydroxide, sodium hydroxide, lithium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, acidic or alkaline buffering agent, etc., which are alkaline are added to the fixing agent part side as necessary. be able to.

  In addition, each processing solution can contain various other fluorescent brightening agents, antifoaming agents, surfactants, polyvinylpyrrolidone, and the like.

The water washing alternative stabilization process following the desilvering process has already been described.
The color development processing method using the additive agent for the water-washing alternative stabilizer of the present invention has been described above. Next, a development processing apparatus that performs the development processing will be described.

The automatic processor preferably used in the present invention described below is a typical embodiment and is not limited thereto.
In the present invention, it is preferable that the linear speed of conveyance of the automatic processor is 100 mm / second or less. It is more preferably 27.8 mm / second to 80 mm / second, particularly preferably 27.8 mm / second to 50 mm / second.

  The color paper automatic processor transports the color paper to the final size and then develops it (sheet type transport method), or develops the paper in a long roll and cuts it to the final size after processing (cine) Mold conveyance system). The cine type conveyance method is preferably a sheet type conveyance method because a photosensitive material of about 2 mm is wasted between images.

The treatment liquid according to the present invention is a treatment tank and a replenishment liquid tank, and it is preferable that the area (opening area) where the liquid comes into contact with air is as small as possible. For example, when the opening ratio is a value obtained by dividing the opening area (cm ² ) by the liquid tank (cm ³ ) in the tank, the opening ratio is preferably 0.01 (cm ⁻¹ ) or less, and more preferably 0.005 or less. In particular, 0.001 or less is most preferable.

In order to reduce the area in contact with air, it is preferable to provide solid or liquid air non-contact means floating on the liquid surface in the treatment tank and the replenishment tank.
Specifically, it is preferable to cover a plastic float or the like on a liquid surface or a liquid that does not mix with the processing liquid and does not cause a chemical reaction. As examples of the liquid, liquid paraffin, liquid saturated hydrocarbon and the like are preferable.

In the present invention, in order to perform processing quickly, the air time when the photosensitive material moves between the processing solutions, that is, the crossover time is preferably as short as possible, preferably 10 seconds or less, more preferably 7 seconds or less, More preferably, it is 5 seconds or less.
Further, in order to shorten the crossover time and prevent the mixing of the processing liquid, a crossover rack structure provided with a mixing prevention plate is preferable.

As a method for eliminating the crossover time at all, it is particularly preferable to use a submerged conveyance structure using a blade described in JP-A-2002-55422. In this method, a crossover time can be reduced to zero by providing a blade between processing tanks to prevent liquid leakage and allowing the photosensitive material to pass therethrough.
It is particularly preferable to install a porous material pleated filter in the liquid circulation structure in which the liquid circulation direction described in Japanese Patent Application No. 2001-147814 is flowed downward in the submerged conveyance structure by the blade and the circulation system.

It is preferable to perform so-called evaporation correction in which water corresponding to the evaporation amount of the processing liquid is supplied to each processing liquid according to the present invention. In particular, it is preferable in a color developer and a bleach-fix solution.
A specific method for performing such water replenishment is not particularly limited, but a monitor water tank different from the bleach-fixing tank described in JP-A-1-254959 and 1-254960 is installed, and the monitor Calculate the amount of water evaporation in the tank, calculate the amount of water evaporation in the bleach-fixing tank from this amount of water evaporation, replenish the water to the bleach-fixing tank in proportion to this amount of evaporation, liquid level sensor, and overflow An evaporation correction method using a sensor is preferred. The most preferable evaporation correction method is to predict and add water corresponding to the amount of evaporation, and is described in the Japanese Institute of Invention and Technology Publication No. 94-49925, page 1, right column, line 26 to page 3, left column, line 28. As described above, the amount of water calculated by a coefficient determined in advance based on the information on the operation time, stop time, and temperature control time of the automatic processor is added.

The drying conditions of the photosensitive material also affect the evaporation of the processing solution. The drying method is preferably a ceramic hot air heater is preferably min 4m ³ to 20 m ³ as feed air volume, particularly 6 m ³ through 10m ³ preferred.
The thermostat for preventing the heating of the ceramic warm air heater is preferably operated by heat transfer, and the mounting position is preferably attached leeward or upwind through the radiating fin or the heat transfer portion. The drying temperature is preferably adjusted according to the water content of the light-sensitive material to be processed. The optimum temperature is 45 to 55 ° C. for an APS format and 35 mm wide film, and 55 to 65 ° C. for a brownie film. The drying time is preferably 5 seconds to 2 minutes, more preferably 5 seconds to 60 seconds.
A replenishment pump is used for replenishing the treatment liquid, but a bellows type replenishment pump is preferable. As a method for improving the replenishment accuracy, it is effective to reduce the diameter of the liquid feeding tube to the replenishing nozzle in order to prevent backflow when the pump is stopped. A preferable inner diameter is 1 to 8 mm, and a particularly preferable inner diameter is 2 to 5 mm.

In general, the processing liquid used in each of the development processing steps is supplied as a processing agent and prepared from the processing agent. The treatment agent is preferably used in the form of a kit in which the treatment agents for each process are combined into a set in addition to the treatment agents for each step individually. In this case, each treatment for the replenisher is also used. It is more preferable that the agent can be attached to or detached from the developing device in the form of a cartridge. The material of these treatment agent containers can be any material such as paper, plastic, metal, etc., but the oxygen permeation coefficient is 57 × 10 ⁻⁶ mL / Pa · m, apart from the treatment agent containing bleach agent. A plastic material of ² · s (50 ml / m ² · atm · day) or less is preferable. The oxygen permeability coefficient "O ₂ permeation of plastic Container, Modern Packing" _{(O 2 permeation of plastic container,} Modern Packing; NJCalyan, 1968) 12 January issue of, pp 143 to 145 It can be measured by the method.
Specific examples of preferable plastic materials include vinylidene chloride (PVDC), nylon (NY), polyethylene (PE), polypropylene (PP), polyester (PES), ethylene-vinyl acetate copolymer (EVA), and ethylene-vinyl. Examples include alcohol copolymer (EVAL), polyacrylonitrile (PAN), polyvinyl alcohol (PVA), polyethylene terephthalate (PET), and the like.
Apart from the bleach-containing treatment agent container, PVDC, NY, PE, EVA, EVAL and PET are preferably used for the purpose of reducing oxygen permeability.

  These materials may be used singly, shaped and used, or may be used in the form of a film and used by bonding a plurality of types (so-called composite film). As the shape of the container, various shapes such as a bottle type, a cubic type and a pillow type can be used. However, the present invention is a cubic type which is flexible and easy to handle and can be reduced in volume after use. A structure similar to is particularly preferred.

Moreover, when using as a composite film, although the thing of the structure shown below is especially preferable, it is not limited to these. That is, PE / EVAL / PE, PE / aluminum foil / PE, NY / PE / NY, NY / PE / EVAL, PE / NY / PE / WVAL / PE, PE / NY / PE / PE / PE / NY / PE PE / SiO ₂ film / PE, PE / PVDC / PE, PE / NY / aluminum foil / PE, PE / PP / aluminum foil / PE, NY / PE / PVDC / NY, NY / EVAL / PE / EVAL / NY NY / PE / EVAL / NY, NY / PE / PVDC / NY / EVAL / PE, PP / EVAL / PE, PP / EVAL / PP, NY / EVAL / PE, NY / aluminum foil / PE, paper / aluminum foil / PE, paper / PE / aluminum foil / PE, PE / PVDC / NY / PE, NY / PE / aluminum foil / PE, PET / EVAL / PE, Examples include PET / aluminum foil / PE, PET / aluminum foil / PET / PE, and the like.

The thickness of the composite film is about 5 to 1500 microns, preferably about 10 to 1000 microns. The inner volume of the finished container is about 100 ml to 20 liters, preferably about 500 ml to 10 liters.
The container (cartridge) may have a cardboard or plastic outer box, or may be formed integrally with the outer box.
The cartridge of the present invention can be filled with various processing solutions. For example, a color developer, black and white developer, bleach solution, adjustment solution, reversal solution, fixing solution, bleach-fix solution, stabilizer, and the like can be mentioned. It is preferable to use a developer, a fixing solution and a bleach-fixing solution.

[Applicable photosensitive material]
Next, the photosensitive material used in the present invention will be described. The photosensitive material used in the present invention is a color photographic photosensitive material for photography, color photographic paper, black-and-white photographic material for photography, and black-and-white photographic paper that is widely used in the photographic market as described above in relation to the object and background of the invention. In this photosensitive material, at least one photosensitive layer is provided on a support. A typical example is a silver halide photographic light-sensitive material having at least one photosensitive layer comprising a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivity on a support. It is.

  In a multilayer silver halide color photographic light-sensitive material for photographing, the photosensitive layer is a unit photosensitive layer having a color sensitivity to any one of blue light, green light, and red light, and is generally an array of unit photosensitive layers. However, the red color-sensitive layer, the green color-sensitive layer, and the blue color-sensitive layer are installed in this order from the support side. However, depending on the purpose, the installation order may be reversed, or the installation order may be such that different photosensitive layers are sandwiched in the same color-sensitive layer. A non-photosensitive layer may be provided between the above-described silver halide photosensitive layers and as the uppermost layer and the lowermost layer. These may contain couplers, DIR compounds, color mixing inhibitors and the like described later. A plurality of silver halide emulsion layers constituting each unit photosensitive layer are sequentially exposed to a support, two layers of a high-sensitivity emulsion layer and a low-sensitivity emulsion layer as described in DE 1,121,470 or GB 923,045. It is preferable to arrange so that the degree is low. Further, as described in JP-A-57-112751, 62-200350, 62-206541, 62-206543, a low-sensitivity emulsion layer on the side away from the support, close to the support A high-sensitivity emulsion layer may be provided on the side.

  In addition, as described in JP-B-49-15495, the upper layer is a silver halide emulsion layer having the highest sensitivity, the middle layer is a silver halide emulsion layer having a lower sensitivity, and the lower layer is more sensitive than the middle layer. Examples include an arrangement composed of three layers having different sensitivities in which a low silver halide emulsion layer is arranged and the sensitivities are gradually lowered toward the support. Even in the case of being composed of three layers having different sensitivities, as described in JP-A-59-202464, the medium-sensitive emulsion layer / high They may be arranged in the order of sensitive emulsion layer / low sensitive emulsion layer.

  In order to improve color reproducibility, the main photosensitive layers such as BL, GL, and RL and spectral sensitivity distribution described in the specifications of US 4,663,271, 4,705,744, 4,707,436, and JP-A-62-160448 and 63-89850 are disclosed. It is preferable to dispose a donor layer (CL) having different multi-layer effects adjacent to or close to the main photosensitive layer.

  A photosensitive material for printing generally uses a reflective support, and is often installed in the order of a red color-sensitive layer, a green color-sensitive layer, and a blue color sensitivity in order from the side far from the support. As the silver halide emulsion, a cubic emulsion of silver chloride or silver chlorobromide grains of high silver chloride is used.

The silver halide photographic emulsion that can be used in the present invention is, for example, Research Disclosure (hereinafter abbreviated as RD) No. 17643 (December 1978), pages 22 to 23, “I. Emulsion preparation and types”. No. 18716 (November 1979), 648, No. 307105 (November 1989), pages 863 to 865, and “Physics and Chemistry of Photography”, published by Paul Monter (P. Glafkides, Chimie et Phisique Photographiques, Paul Montel, 1967), "Photoemulsion Chemistry" by Duffin, published by Focal Press (GF Duffin, Photographic Emulsion Chemistry, Focal Press, 1966), "Production and Coating of Photoemulsions" , Published by Focal Press (VL Zelikman, et al., Making and Coating Photographic Emulsion, Focal Press, 1964) and the like. Monodisperse emulsions described in US Pat. Nos. 3,574,628, 3,655,394 and GB 1,413,748 are also preferable.
Photographic additives that can be used in color light-sensitive materials are also described in the RD, and the description locations related to the following table are shown.

Type of additive RD17643 RD18716 RD3071051.
Chemical sensitizer 23 pages 648 pages right column 866 pages
Sensitivity enhancer 648, right column Spectral sensitizer, pages 23-24 24 648, right column 866-868 pages Supersensitizer 649 pages, right column Whitening agent 24 pages 647, right column 868 Light absorber, 25 ~ 26 pages, 649 pages, right column, pages 873
Filter, Dye, ~ 650 page left column
UV absorber Binder 26 pages 651 pages left column 873-874 plasticizers page 27 650 pages right column page 876
Lubricant Application aid, page 26-27, page 650, right column, page 875-876 Surface active agent Antistatic agent page 27, page 650, right column, page 876-877 page Matte agent, pages 878-879.

<Exposure>
Next, as a printer for producing a print by development using the processing composition of the present invention, a general-purpose printer is used. In addition to being used in a printing system using a normal negative printer, a cathode ray ( It is also suitable for a scanning exposure method using CRT). A cathode ray tube exposure apparatus is more convenient and compact than an apparatus using a laser, and is low in cost. Also, the adjustment of the optical axis and color is easy. As the cathode ray tube used for image exposure, various light emitters that emit light in the spectral region are used as necessary. For example, any one of red light emitters, green light emitters, and blue light emitters, or a mixture of two or more thereof may be used. The spectral region is not limited to the above red, green, and blue, and a phosphor that emits light in the yellow, orange, purple, or infrared region is also used. In particular, a cathode ray tube that emits white light by mixing these light emitters is often used.

  The photosensitive material used in the present invention is a monochromatic light source such as a gas laser, a light emitting diode, a semiconductor laser, a semiconductor laser, or a second harmonic generation light source (SHG) that combines a solid-state laser using a semiconductor laser as an excitation light source and a nonlinear optical crystal. It is preferably used in a digital scanning exposure method using high density light. In order to make the system compact and inexpensive, it is preferable to use a second harmonic generation light source (SHG) that combines a semiconductor laser, a semiconductor laser, or a solid-state laser and a nonlinear optical crystal. In particular, in order to design a compact, inexpensive, long-life and high-stability device, it is preferable to use a semiconductor laser, and at least one of the exposure light sources is preferably a semiconductor laser.

  Preferred scanning exposure methods applicable to the present invention are described in detail in the patents listed in the table above. In order to process the light-sensitive material by the method of the present invention, JP-A-2-207250, page 26, lower right column, line 1 to page 34, upper-right column, line 9 and JP-A-4-97355, The processing materials and processing methods described in page 17, upper left column, line 17 to page 18, lower right column, line 20 are preferably applicable.

EXAMPLES Hereinafter, although an Example demonstrates this invention more concretely, these do not limit the scope of the present invention at all.
Example-1
EXAMPLES Hereinafter, although an Example demonstrates this invention more concretely, these do not limit the scope of the present invention at all.

-Light-sensitive material used in the test (preparation of blue-sensitive layer emulsion BH-1)
High silver chloride cubic particles were prepared by a method in which silver nitrate and sodium chloride were simultaneously added to and mixed with deionized distilled water containing stirred deionized gelatin. In the course of this preparation, Cs ₂ [OsCl ₅ (NO)] was added from 60% to 80% addition of silver nitrate. From the 80% to 90% addition of silver nitrate, potassium bromide (1.5 mol% per mole of finished silver halide) and K ₄ [Fe (CN) ₆ ] were added. K ₂ [IrCl ₆ ] was added from 83% to 88% addition of silver nitrate. K ₂ [IrCl ₅ (H ₂ O)] and K [IrCl ₄ (H ₂ O) ₂ ] were added from 92% to 98% addition of silver nitrate. When 94% of the addition of silver nitrate was completed, potassium iodide (0.27 mol% per mol of the finished silver halide) was added with vigorous stirring. The obtained emulsion grains were monodispersed cubic silver iodobromochloride grains having a side length of 0.54 μm and a coefficient of variation of 8.5%. This emulsion was subjected to precipitation desalting treatment, and gelatin, compounds Ab-1, Ab-2, Ab-3, and calcium nitrate were added thereto and redispersed.

  The redispersed emulsion was dissolved at 40 ° C., and sensitizing dye S-1, sensitizing dye S-2, and sensitizing dye S-3 of the present invention were added so as to optimize spectral sensitization. Next, sodium benzenethiosulfate, triethylthiourea as a sulfur sensitizer, and compound-1 as a gold sensitizer were added and ripened so as to optimize chemical sensitization. Thereafter, a compound in which the repeating unit 2 or 3 represented by 1- (5-methylureidophenyl) -5-mercaptotetrazole, compound-2, compound-3 is a main component (terminal X1 and X2 are hydroxyl groups), compound- 4 and potassium bromide were added to terminate the chemical sensitization. The emulsion thus obtained was designated as Emulsion BH-1.

(Preparation of blue-sensitive layer emulsion BL-1)
In preparation of emulsion BH-1, the temperature and the addition speed of the step of adding and mixing silver nitrate and sodium chloride at the same time were changed, and the amounts of various metal complexes added during the addition of silver nitrate and sodium chloride were changed. Thus, emulsion grains were obtained. The emulsion grains were monodispersed cubic silver iodobromochloride grains having a side length of 0.44 μm and a coefficient of variation of 9.5%. After redispersing this emulsion, Emulsion BL-1 was prepared in the same manner except that the amount of various compounds added was changed from that of BH-1.

(Preparation of green sensitive layer emulsion GH-1)
High silver chloride cubic particles were prepared by a method in which silver nitrate and sodium chloride were simultaneously added to and mixed with deionized distilled water containing stirred deionized gelatin. In the course of this preparation, K ₄ [Ru (CN) ₆ ] was added from 80% to 90% addition of silver nitrate. Potassium bromide (2 mol% per mole of finished silver halide) was added from the point where the addition of silver nitrate was 80% to 100%. K ₂ [IrCl ₆ ] and K ₂ [RhBr ₅ (H ₂ O)] were added from 83% to 88% addition of silver nitrate. When 90% of the addition of silver nitrate was completed, potassium iodide (0.1 mol% per mol of the finished silver halide) was added with vigorous stirring. Further, K ₂ [IrCl ₅ (H ₂ O)] and K [IrCl ₄ (H ₂ O) ₂ ] were added when the addition of silver nitrate was 92% to 98%. The obtained emulsion grains were monodispersed cubic silver iodobromochloride grains having a side length of 0.42 μm and a coefficient of variation of 8.0%. This emulsion was subjected to precipitation desalting and redispersion in the same manner as described above.

  This emulsion was dissolved at 40 ° C. and sodium benzenethiosulfate, p-glutaramide phenyl disulfide, sodium thiosulfate pentahydrate as a sulfur sensitizer and (bis (1,4,5-trimethyl-1) as a gold sensitizer. , 2,4-triazolium-3-thiolate) orate (I) tetrafluoroborate) and ripened to optimize chemical sensitization. Thereafter, 1- (3-acetamidophenyl) -5-mercaptotetrazole, 1- (5-methylureidophenyl) -5-mercaptotetrazole, compound-2, compound-4 and potassium bromide were added. Furthermore, spectral sensitization was performed by adding sensitizing dyes S-4, S-5, S-6 and S-7 as sensitizing dyes during the emulsion preparation process. The emulsion thus obtained was designated as Emulsion GH-1.

(Preparation of green-sensitive layer emulsion GL-1)
In preparation of Emulsion GH-1, the temperature and rate of addition of silver nitrate and sodium chloride are added and mixed, and the amount of various metal complexes added during the addition of silver nitrate and sodium chloride is changed. Thus, emulsion grains were obtained. The emulsion grains were monodispersed cubic silver iodobromochloride grains having a side length of 0.35 μm and a coefficient of variation of 9.8%. After redispersing this emulsion, Emulsion GL-1 was similarly prepared except that the amount of various compounds added was changed from that of Emulsion GH-1.

(Preparation of emulsion RH-1 for red-sensitive layer)
High silver chloride cubic particles were prepared by a method in which silver nitrate and sodium chloride were simultaneously added to and mixed with deionized distilled water containing stirred deionized gelatin. In the course of this preparation, Cs ₂ [OsCl ₅ (NO)] was added from 60% to 80% addition of silver nitrate. K ₄ [Ru (CN) ₆ ] was added from the time point when the addition of silver nitrate was 80% to 90%. Potassium bromide (1.3 mol% per mol of finished silver halide) was added from the 80% to 100% addition of silver nitrate. K ₂ [IrCl ₅ (5-methylthiazole)] was added from 83% to 88% when silver nitrate was added. When the addition of silver nitrate was completed 88%, potassium iodide (amount of silver iodide to be 0.05 mol% per mol of finished silver halide) was added with vigorous stirring. Further, K ₂ [IrCl ₅ (H ₂ O)] and K [IrCl ₄ (H ₂ O) ₂ ] were added when the addition of silver nitrate was 92% to 98%. The obtained emulsion grains were monodispersed cubic silver iodobromochloride emulsion grains having a cube side length of 0.39 μm and a coefficient of variation of 10%. The obtained emulsion was subjected to precipitation desalting and redispersion in the same manner as described above.

  This emulsion is dissolved at 40 ° C., and sensitizing dye S-8, compound-5, triethylthiourea as sulfur sensitizer and compound-1 as gold sensitizer are added to optimize chemical sensitization. Aged. Thereafter, 1- (3-acetamidophenyl) -5-mercaptotetrazole, 1- (5-methylureidophenyl) -5-mercaptotetrazole, compound-2, compound-4, and potassium bromide were added. The emulsion thus obtained was designated as Emulsion RH-1.

増感色素Ｓ−８

Sensitizing dye S-8

化合物−５

Compound-5

(Preparation of emulsion RL-1 for red-sensitive layer)
In preparation of emulsion RH-1, the temperature and rate of addition of silver nitrate and sodium chloride are added and mixed, and the amounts of various metal complexes added during the addition of silver nitrate and sodium chloride are changed. Thus, emulsion grains were obtained. The emulsion grains were monodispersed cubic silver iodobromochloride grains having a side length of 0.29 μm and a coefficient of variation of 9.9%. Emulsion RL-1 was prepared in the same manner except that the amount of various compounds added was changed from that of Emulsion RH-1 after precipitation desalting treatment and maximum dispersion.

Preparation of first layer coating solution 34 g of yellow coupler (ExY-1), 1 g of color image stabilizer (Cpd-1), 1 g of color image stabilizer (Cpd-2), 8 g of color image stabilizer (Cpd-8), color image 1 g of stabilizer (Cpd-18), 2 g of color image stabilizer (Cpd-19), 15 g of color image stabilizer (Cpd-20), 1 g of color image stabilizer (Cpd-21), color image stabilizer (Cpd-23) 15 g, 0.1 g additive (ExC-1), 1 g color image stabilizer (UV-2) 23 g solvent (Solv-4), 4 g solvent (Solv-6), 23 g solvent (Solv-9) and acetic acid Dissolve in 60 ml of ethyl, and emulsify and disperse this liquid in 270 g of a 20% by weight gelatin aqueous solution containing 4 g of sodium dodecylbenzenesulfonate using a high-speed stirring emulsifier (dissolver), and add 900 g of emulsion dispersion A by adding water. did.
On the other hand, the emulsified dispersion A and the emulsions BH-1 and BL-1 were mixed and dissolved to prepare a first layer coating solution having a composition described later. The emulsion coating amount indicates the silver coating amount.

The coating solutions for the second to seventh layers were prepared in the same manner as the first layer coating solution. As the gelatin hardener for each layer, 1-oxy-3,5-dichloro-s-triazine sodium salt (H-1), (H-2), (H-3) was used. Further, each layer Ab-1, Ab-2, and Ab-3 the total amount each ^{15.0mg / m 2, 60.0mg / m} 2, 5.0mg / m 2 and 10.0 mg / ^{m 2} and so as Added to.

1- (3-Methylureidophenyl) -5-mercaptotetrazole was added to the second, fourth and sixth layers, 0.2 mg / m ² , 0.2 mg / m ² and 0.6 mg / m ^{2 respectively.} It added so that it might become. For the blue-sensitive emulsion layer and the green-sensitive emulsion layer, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene is respectively 1 × 10 ⁻⁴ mol, 2 ×, per mol of silver halide. ^10-4 mol was added. 0.05 g / m ² of a copolymer latex of methacrylic acid and butyl acrylate (weight ratio 1: 1, average molecular weight 200,000 to 400,000) was added to the red sensitive emulsion layer. The second layer, was added the fourth layer and the sixth layer in disodium catechol-3,5-disulfonate as respectively a ^{6mg / m 2, 6mg / m} 2, 18mg / m 2.
Sodium polystyrene sulfonate was added to each layer as necessary to adjust the viscosity of the coating solution. In order to prevent irradiation, the following dyes were added (the amount in parentheses represents the coating amount).

(Layer structure)
The structure of each layer is shown below. The numbers represent the coating amount (g / m ² ). The silver halide emulsion represents a coating amount in terms of silver.
Support: Polyethylene resin laminated paper [White pigment (TiO ₂ ; content: 16% by weight, ZnO; content: 4% by weight), polyethylene brightening agent (4,4′-bis (5- Methylbenzoxazolyl) stilbene (content 0.03% by weight) and bluish dye (ultraviolet, content 0.33% by weight) .The amount of polyethylene resin is 29.2 g / m ² )
First layer (blue photosensitive emulsion layer)
Emulsion (5: 5 mixture of BH-1 and BL-1 (silver molar ratio)) 0.16
Gelatin 1.32
Yellow coupler (EX-Y) 0.34
Color image stabilizer (Cpd-1) 0.01
Color image stabilizer (Cpd-2) 0.01
Color image stabilizer (Cpd-8) 0.08
Color image stabilizer (Cpd-18) 0.01
Color image stabilizer (Cpd-19) 0.02
Color image stabilizer (Cpd-20) 0.15
Color image stabilizer (Cpd-21) 0.01
Color image stabilizer (Cpd-23) 0.15
Additive (ExC-1) 0.001
Color image stabilizer (UV-A) 0.01
Solvent (Solv-4) 0.23
Solvent (Solv-6) 0.04
Solvent (Solv-9) 0.23

Second layer (color mixing prevention layer)
Gelatin 0.78
Color mixing inhibitor (Cpd-4) 0.05
Color mixing inhibitor (Cpd-12) 0.01
Color image stabilizer (Cpd-5) 0.006
Color image stabilizer (Cpd-6) 0.05
Color image stabilizer (UV-A) 0.06
Color image stabilizer (Cpd-7) 0.006
Preservative (Cpd-24) 0.006
Solvent (Solv-1) 0.06
Solvent (Solv-2) 0.06
Solvent (Solv-5) 0.07
Solvent (Solv-8) 0.07

Third layer (green photosensitive emulsion layer)
Emulsion (1: 3 mixture of GH-1 and GL-1 (silver molar ratio)) 0.12
Gelatin 0.95
Magenta coupler (ExM) 0.12
UV absorber (UV-A) 0.03
Color image stabilizer (Cpd-2) 0.01
Color image stabilizer (Cpd-6) 0.08
Color image stabilizer (Cpd-7) 0.005
Color image stabilizer (Cpd-8) 0.01
Color image stabilizer (Cpd-9) 0.01
Color image stabilizer (Cpd-10) 0.005
Color image stabilizer (Cpd-11) 0.0001
Color image stabilizer (Cpd-20) 0.01
Solvent (Solv-3) 0.06
Solvent (Solv-4) 0.12
Solvent (Solv-6) 0.05
Solvent (Solv-9) 0.16

Fourth layer (color mixing prevention layer)
Gelatin 0.65
Color mixing inhibitor (Cpd-4) 0.04
Color mixing inhibitor (Cpd-12) 0.01
Color image stabilizer (Cpd-5) 0.005
Color image stabilizer (Cpd-6) 0.04
Color image stabilizer (UV-A) 0.05
Color image stabilizer (Cpd-7) 0.005
Preservative (Cpd-24) 0.005
Solvent (Solv-1) 0.05
Solvent (Solv-2) 0.05
Solvent (Solv-5) 0.06
Solvent (Solv-8) 0.06

5th layer (red photosensitive emulsion layer)
Emulsion (4: 6 mixture of RH-1 and RL-1 (silver molar ratio)) 0.10
Gelatin 1.11
Cyan coupler (ExC-1) 0.11
Cyan coupler (ExC-2) 0.01
Cyan coupler (ExC-3) 0.04
Color image stabilizer (Cpd-1) 0.03
Color image stabilizer (Cpd-7) 0.01
Color image stabilizer (Cpd-9) 0.04
Color image stabilizer (Cpd-10) 0.001
Color image stabilizer (Cpd-14) 0.001
Color image stabilizer (Cpd-15) 0.18
Color image stabilizer (Cpd-16) 0.002
Color image stabilizer (Cpd-17) 0.001
Color image stabilizer (Cpd-18) 0.05
Color image stabilizer (Cpd-19) 0.04
Color image stabilizer (UV-5) 0.10
Solvent (Solv-5) 0.19

Sixth layer (UV absorbing layer)
Gelatin 0.34
Ultraviolet absorber (UV-B) 0.24
Compound (S1-4) 0.0015
Solvent (Solv-7) 0.11
Compound (S1-4) 0.0015
Solvent (Solv-7) 0.11

Seventh layer (protective layer)
Gelatin 0.82
Additive (Cpd-22) 0.03
Liquid paraffin 0.02
Surfactant (Cpd-13) 0.02

  The sample prepared as described above was designated as Sample 001.

2. Development processing test The sample 001 was processed into a 127 mm width roll, and a standard photographic image was exposed using a minilab printer processor MSC101 (Agfa). Thereafter, continuous processing (running test) was performed in the following processing steps until the volume of the color developer replenisher became twice the volume of the color developer tank. The stabilizer additive solution was added in the amount shown in Table 1 to the tank solution and the replenisher solution at the start of continuous processing.

Processing temperature Temperature Time Replenishment amount
Color development 38.0 ° C 33 seconds 70 mL
Bleach fixing 35.0 ℃ 33 seconds 110mL
Stable 1 35.0 ° C 19 seconds-
Stability 2 35.0 ° C 19 seconds-
Stable 3 35.0 ° C 19 seconds-
Stability 4 35.0 ° C 19 seconds 250 mL
Dry 80 ° C
(note)
* Replenishment rate per photosensitive material 1 m ² · * stable was a four-tank counter-current system from (1) to (4).

The composition of each treatment liquid is as follows.
[Color developer] [Tank solution] [Replenisher]
800 ml of water 800 ml
Diethylene glycol 5.0 g 5.0 g
ε-Caprolactam 20.0 g 20.0 g
Optical brightener (FL-1) 1.0g 2.0g
Fluorescent brightener (WHITEX-4) 0.5g 2.0g
Residual color reducing agent (SR-1) 1.0 g 3.0 g
Sodium p-toluenesulfonate 5.0 g 5.0 g
Ethylenediaminetetraacetic acid 3.0 g 3.0 g
Sodium sulfite 0.10g 0.10g
Potassium chloride 3.0g ―
4,5-dihydroxybenzene-
Sodium 1,3-disulfonate 0.30 g 0.30 g
N, N-diethylhydroxylamine 2.0 g 5.0 g
Disodium-N, N-bis (sulfonate ethyl) hydroxylamine 4.0 g 5.0 g
4-Amino-3-methyl-N-ethyl-N-
(Β-Methanesulfonamidoethyl) aniline
・ 3/2 sulfate ・ Monohydride 4.5g 10.0g
Potassium carbonate 26.3g 26.3g
Add water for a total volume of 1000 mL 1000 mL
pH (adjusted with sulfuric acid and KOH at 25 ° C) 10.25 12.0

[Bleaching fixer] [Tank solution] [Replenisher]
Water 800mL 600mL
Citric acid 1.0g 2.0g
Sulfosuccinic acid 1.0 g 2.0 g
Ethylenediaminetetraacetic acid iron (III)
Ammonium 40.0g 50.0g
Ethylenediaminetetraacetic acid 2.5 g 3.0 g
Potassium dihydrogen phosphate 5.0 g 10.0 g
Nitric acid (67%) 5.0 g 10.0 g
m-Carboxysulfinic acid 5.0 g 5.0 g
Ammonium thiosulfate (70%) 100.0 mL 130.0 mL
Ammonium sulfite 30.0g 40.0g
Add water for a total volume of 1000 mL 1000 mL
pH (adjusted with 25 ° C, nitric acid and aqueous ammonia) 6.30 5.50

[Stabilizer] [Common tank and replenisher]
Sodium sulfite See Table 1
Hydroxyethane diphosphonate disodium 2.0g
Ethylenediaminetetraacetate disodium 2.0g
Sodium benzoate 0.5g
1000mL
pH (25 ° C.) 8.0

[Stable liquid additive liquid]
700ml of water
Ammonium sulfate See Table 1 1,2-Benzothiazolin-3-one See Table 1 Add water for a total volume of 1000 mL
pH (adjusted with nitric acid and aqueous ammonia at 25 ° C) 6.00

At the end of the continuous treatment, the following measurements were performed using the treated color vapor, and the results are shown in Table 1.
-Store the sensitive material for 10 days at 80 ° C / 70% RH, and change the maximum density of cyan before and after storage.-Minimum yellow density of the processed photosensitive material.-Stain of the squeeze roller in the processor stabilizer. Presence or absence of suspended matter inside

Experiment No. which is a comparative example. No. 1 has a relatively low cyan amber color, but has a high minimum yellow density, and many roller stains and floating matters are generated. Experiment No. which is a comparative example. Nos. 2 to 4 and 8 have a large cyan amber color and are serious problems in practice.
No. of the present invention. Nos. 5 to 7 had very little cyan fading, a low yellow minimum density, and at the same time, no roller smearing or floating matter was generated, and good results were obtained.
In the present invention, when 100 ppm of 1,2-benzothiazolin-3-one in the stable additive liquid is contained, a better result is obtained in that the generation of suspended matters can be completely prevented.

Claims (5)

  A processing composition to be added as an additive to an alkali metal sulfite-containing water-washing alternative stabilizer and / or water-washing alternative stable replenisher for processing silver halide color photographic light-sensitive materials, characterized by containing ammonium sulfate Alternative additive for stabilizers.   The additive agent for an alternative stabilizer for washing according to claim 1, wherein the content of ammonium sulfate is 1.0 to 5.0 mol / L.   Further, 1,2-benzothiazolin-3-one is contained in an amount of 20 to 200 mg / L.   Halogen, characterized in that the additive agent according to any one of claims 1 to 3 is added to a water-washing alternative stabilizer and / or water-washing alternative replenisher containing an alkali metal sulfite salt for processing silver halide color photographic materials. Processing method of silver halide color photographic light-sensitive material.   5. The processing of a silver halide color photographic light-sensitive material according to claim 4, wherein the concentration of ammonium sulfate in the water-washing alternative stabilizer and / or the water-washing alternative stable replenisher is 1.0 to 10.0 mmol / L. Method.