JP2006259316A - Replenishment water supply device of automatic developing machine for silver halide color photosensitive material and method for processing silver halide color photosensitive material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a replenishment water supply device of an automatic developing machine for a silver halide color photosensitive material provided with a silver ion elution means in which no water stain is generated in a water replenishment tank, and in which the influence on the photographic performance is extremely little even when the replenishment water in the water replenishment tank is supplied to each processing chamber, and to provide a method for processing a silver halide color photosensitive material using the same. <P>SOLUTION: In the method for processing the silver halide color photosensitive material, the silver halide color photosensitive material is processed by replenishing the replenishment water containing the silver ions eluted by the silver ion elution means in the water replenishment tank to at least one processing chamber of the automatic developing machine. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention is a photograph of a water replenisher supplying device and a water replenishing tank of an automatic developing machine for silver halide light-sensitive material provided with silver ion eluting means. The present invention relates to a method for processing a silver halide color light-sensitive material having a very small influence on performance.

  Silver halide color light-sensitive materials are widely used today because of their high sensitivity, excellent color reproducibility, and suitability for continuous processing. For silver halide color photographic materials for general photography that have been widely used in the past, for example, in a method of photographing with a color negative film and printing a color image obtained through a development process using an optical system, the printing conditions are set in advance. With this setting, the printing conditions are easily determined and adjusted based on the result of measuring the density of the color negative film, and the color print photosensitive material (color photographic paper) is a full-color excellent color image with a single exposure. This is a system that can obtain print images continuously and has extremely high productivity. In addition, this color photographic paper has recently been used in a digital image forming method for forming a color image by modulating the amount of light from an exposure light source such as a laser or LED by image data taken with a digital camera or the like. . Also in digital image exposure, normally, modulated three-color lights of B, G, and R are mixed, and a color image is formed by one scan, which shows high productivity similar to the conventional one.

  In addition, recording materials using silver halide color light-sensitive materials are known to have low noise, particularly at low densities, and have characteristics that enable very smooth gradation reproduction. When the apparatus has a sufficient gradation reproduction capacity, it has a feature that it is excellent in highlight delineability. Because of these characteristics, silver halide color light-sensitive materials are widely used not only in the field of photography, but also in the field of printing, in the field of so-called color proofing for checking the state of finished prints in the middle of printing. It is becoming.

  In the field of proofing, a color image edited on a computer is output to a printing film, and the developed film is subjected to separation exposure while appropriately replacing the film, whereby yellow (Y), magenta (M), cyan (C ), And an image of the final printed matter is formed on color photographic paper, thereby determining the layout and color suitability of the final printed matter.

  Recently, a method of directly outputting an image edited on a computer to a printing plate has gradually become widespread, and in such a case, a color image can be obtained directly from the data on the computer without using a film. It was desired.

  For this purpose, various methods such as a sublimation type / melting heat transfer method, an electrophotographic method, and an ink jet method have been tried. However, a method capable of obtaining a high-quality image is expensive and inferior in productivity. In addition, there is a disadvantage that the image quality is inferior in a method that is low in cost and excellent in productivity.

  The system using silver halide color photosensitive material enables high-quality image formation, such as the ability to form an accurate halftone image due to excellent sharpness, etc. On the other hand, continuous development processing is possible as described above. High productivity can be realized from the standpoints that images can be simultaneously written to a plurality of color image forming units.

  When a silver halide color light-sensitive material is used as a color proof, one of the important performances required is white background characteristics. The design that enables the solid density of the color proof produced by the above-described silver halide color light-sensitive material to be as high as necessary is, in other words, a method that can cause deterioration of the white background.

  The development processing of silver halide color light-sensitive materials, which are color proofs, is often carried out using an automatic processor. Such an automatic processor is usually followed by a color development step and a bleach-fixing step, followed by a washing step or a stable step. In general, liquid processing is performed using a processing tank, and many of them are replenished with each replenisher according to the processing amount of the silver halide color light-sensitive material. A method of performing continuous processing is employed.

  In such a continuous processing process, gelatin and organic substances are eluted from the silver halide color light-sensitive material to be developed in each processing solution and stay for a long time. Is in a eutrophic state. For this reason, bacteria and moss are gradually propagated, and so-called scale is generated. If the cleaning is not performed for a long period of time, the generated water scale is transferred as a stain on the silver halide color light-sensitive material to be subjected to development processing, or may cause a conveyance failure in some cases.

  In continuous processing while replenishing each replenisher according to the processing amount of the silver halide color light-sensitive material, in a color developing tank, a bleach-fixing tank, a washing tank or a stabilization tank kept at a constant processing temperature, it is continuous. Since water evaporates according to the treatment, it is necessary to replenish water (hereinafter referred to as supplementary water or correction water) that matches the amount of evaporated water in order to prevent fluctuations in treatment characteristics due to concentration of each treatment liquid. However, depending on the operating time of the automatic processor, the water in the replenishing tank is replenished. If the water in the replenishing tank stays for a long period of time, scales will be generated due to the growth of bacteria and fungi, When water containing water or scale is supplied to the automatic processor, scale adheres to the silver halide color photosensitive material in each processing layer. Further, when the generation of bacteria and fungi occurs particularly in the color developer used in the color development process, it may cause fogging. When the silver halide color light-sensitive material is used as a color proof, the increase in fog density due to such continuous processing adversely affects the white background characteristics, which is one of the important performances required, and impairs the quality. It is a factor.

  Conventionally, it is known to use an antifungal agent as a means for preventing the generation of bacteria and moss generated in a treatment tank and a replenishing tank. For example, with respect to the growth of bacteria due to an increase in residence time in a replenishing tank, a washing step or a stabilization step, JP-A-62-288838 discloses a method for reducing calcium and magnesium, and JP-A-57-8542 discloses Isothiazolone compounds and siabendazoles, JP-A 61-120145 discloses a chlorine-based disinfectant such as chlorinated sodium isocyanurate, and JP-A 63-122516 discloses a method of adding benzotriazole and copper ions. In addition, Hiroshi Horiguchi, “Chemistry of Antibacterial and Antifungal” (1986) Sankyo Publishing, Hygiene Technology Association “Sterilization, Sterilization and Antifungal Technology of Microorganism” (1982) Japan Society for Industrial Technology, Japan It is also known to use the bactericides described in “Encyclopedia of Antibacterial and Antifungal Agents” (1986) edited by the Society of Acupuncture.

  Furthermore, a method is disclosed in which a chlorine-based disinfectant such as an isothiazolone compound or chlorinated isocyanurate sodium is used as a stabilizing solution (see, for example, Patent Document 1). In addition, a treatment method using a stabilizing liquid containing aminopolycarboxylic acids, sulfites, salicylates, and dehydroacetic acid is disclosed, which is said to be effective in the antifungal property of the stabilizing liquid (see, for example, Patent Document 2). .) Moreover, the method of preventing a water scale using an oxidizing agent at the water washing process is disclosed (for example, refer patent document 3). Furthermore, a method for preventing the generation of scale using an active chlorine-based disinfectant or an active bromine-based disinfectant as a stabilizing solution is also known. Any of the above proposed methods is aimed at the antibacterial effect in the water washing step or the stabilization step which is the final step of the development processing, and some of these proposed compounds are color developing solutions. There are many things that affect the development characteristics when added to, and there is no suggestion about a method to prevent the generation of bacteria and moss in the color developer while replenishing silver ion water from the replenishing tank .

  Furthermore, a method is known in which an active halogen fungicide, an isothiazoline fungicide, or a phenol fungicide is added to a stabilizing solution (see, for example, Patent Documents 4 and 5). Although these bactericides have some antibacterial effect, they have the problem of adding white color to the color developer and cause white turbidity, and are stable without affecting development characteristics during continuous processing. In addition, the development of technology that can efficiently prevent the occurrence of water scale is eagerly desired.

On the other hand, with the aim of preventing the generation of scale in the washing tank of the automatic processor, a method for preventing the scale from washing with silver ions is a large-scale washing method in which the replenishing amount of washing water is 0.5 L or more per 1 m ^{2 of} silver halide photosensitive material. Although it is described (for example, see Patent Document 6), there is a description of a method for preventing generation of scale while replenishing silver ion water from a replenishing tank to a color developing tank, and a description of its effect on photographic performance. I can't see it at all.

As described above, there has been no known effective means for preventing the water in the replenishing water tank supplied to the color developing tank.
Japanese Patent Publication No.7-119981 JP-A-8-248589 JP-A-4-276745 Japanese Patent Laid-Open No. 10-221830 Japanese Patent Laid-Open No. 2004-212936 JP-A-2-269339

  The present invention has been made in view of the above problems, and its purpose is that there is no generation of scale in the refill tank, and even if the replenisher in the refill tank is replenished to each processing tank, the effect on the photographic performance is extremely small. An object of the present invention is to provide a water replenisher supply device for an automatic developing machine for silver halide light-sensitive materials provided with silver ion eluting means and a method for processing a silver halide color light-sensitive material using the same.

  The above object of the present invention is achieved by the following configurations.

(Claim 1)
A water replenisher supply device for an automatic developing machine for silver halide color light-sensitive materials, characterized in that silver ion elution means is provided in the water replenishment tank.

(Claim 2)
2. The replenishing solution supply of an automatic processor for silver halide color photographic materials according to claim 1, wherein said silver ion elution means is a silver elution cartridge constituted by a porous film carrying a hardly soluble silver compound. apparatus.

(Claim 3)
2. A replenisher supplying apparatus for an automatic processor for silver halide color photographic materials according to claim 1, wherein said silver ion elution means is a silver elution cartridge composed of silver-impregnated activated carbon.

(Claim 4)
2. A replenisher supplying apparatus for an automatic processor for silver halide color photographic materials according to claim 1, wherein said silver ion elution means is a silver elution cartridge composed of silver plated fibers.

(Claim 5)
2. A replenisher supplying apparatus for an automatic processor for silver halide color photographic materials according to claim 1, wherein said silver ion eluting means is an electrolytic silver ion eluting apparatus.

(Claim 6)
A silver halide color photographic material is processed by replenishing at least one processing tank of an automatic processor with a replenishing liquid containing silver ions eluted from a silver ion elution means in a replenishing tank. Processing method of silver color photosensitive material.

(Claim 7)
7. The method for processing a silver halide color photographic material according to claim 6, wherein the processing tank for replenishing the replenishing solution containing silver ions is a color developing tank.

(Claim 8)
7. The method for processing a silver halide color photographic material according to claim 6, wherein the processing tank for replenishing the replenishing solution containing silver ions is a color developing tank, a bleach-fixing tank, a washing tank or a stabilizing tank.

(Claim 9)
9. The silver halide color photosensitive material according to claim 6, wherein the silver ion elution means is a silver elution cartridge composed of a porous film carrying a hardly soluble silver compound. Processing method.

(Claim 10)
9. The method for processing a silver halide color photographic material according to claim 6, wherein the silver ion elution means is a silver elution cartridge constituted by silver-impregnated activated carbon.

(Claim 11)
9. The method for processing a silver halide color light-sensitive material according to claim 6, wherein the silver ion elution means is a silver elution cartridge composed of silver-plated fibers.

(Claim 12)
9. The method for processing a silver halide color photographic material according to claim 6, wherein the silver ion eluting means is an electrolytic silver ion eluting device.

(Claim 13)
The silver halide color photosensitive material processing method according to any one of claims 6 to 12, wherein a silver ion concentration of the replenishing liquid is 10 ppb or more and 1000 ppb or less.

  According to the present invention, there is no generation of scale in the water replenishing tank, and the silver halide light-sensitive material provided with the silver ion elution means having a very small influence on the photographic performance even if the water is replenished to each processing tank. And a processing method for a silver halide color light-sensitive material using the same.

  Hereinafter, the best mode for carrying out the present invention will be described in detail.

  As a result of intensive studies in view of the above problems, the inventor of the present invention is as follows. 1) A replenishing liquid supply device for an automatic developing machine for silver halide color light-sensitive materials, characterized in that a silver ion elution means is provided in the replenishing tank. 2) A silver halide color characterized in that a silver halide color light-sensitive material is processed by replenishing a processing tank of an automatic processor with a water replenishing solution containing silver ions eluted from a silver ion elution means in a water replenishing tank. Depending on the processing method of the photosensitive material, there is no generation of scale in the replenishing tank, and even if the replenishing solution in the replenishing tank is replenished to each processing tank, it has a silver ion elution means that has extremely little effect on photographic performance. It has been found that a replenisher supply device for an automatic processor for materials and a processing method for a silver halide color photographic material using the same can be realized, and the present invention has been achieved.

  Details of the present invention will be described below.

  First, the automatic developing machine for silver halide color photographic materials and the replenisher supply device of the present invention will be described.

  The silver halide color light-sensitive material automatic developing machine that can be used in the present invention includes at least a color development processing step having a color development processing tank, a bleach-fixing processing step having a bleach-fixing tank, a water-washing processing process having a water-washing tank or a stable It is preferable that it is comprised from the stabilization process process which has a stabilization tank, Among them, the washing process process which has a washing tank or the stabilization process process which has a stabilization tank is comprised from several treatment tanks, and each treatment tank It is preferable to use a multi-stage countercurrent system in which the overflow liquid is brought into a pre-bath treatment tank.

  FIG. 1 is a schematic configuration diagram showing an example of a development processing unit of an automatic processor that can be used in the present invention.

  In FIG. 1A, an automatic processor 8 develops a silver halide color photosensitive material P conveyed from an automatic exposure unit (not shown) while conveying it at a constant speed. In order to process the color photosensitive material P, a processing liquid container for storing a processing liquid to be brought into contact with the silver halide color photosensitive material P was connected to a plurality of liquid tanks 1 and the liquid tank 1 as shown below. The auxiliary tank 2 is provided side by side. That is, in a part of a color developer container storing a color developer to be brought into contact with the silver halide color photosensitive material P in order to perform color development processing on the silver halide color photosensitive material P exposed in the automatic exposure unit. Bleach for storing a bleach-fixing solution to be brought into contact with the silver halide color photosensitive material P in order to bleach-fix the color development tank 1A and the color development auxiliary tank 2A, and the color-developed silver halide color photosensitive material P In order to wash or stabilize the bleach-fixing tank 1B and the bleach-fixing auxiliary tank 2B, which are part of the fixer container, and the bleach-fixed silver halide color photosensitive material P, contact the silver halide color photosensitive material P. Stabilization tanks 1C, 1D, and 1E that are part of a plurality of flushing or stabilizing liquid containers connected in a multi-stage countercurrent system for storing flushing water or stabilizing liquid The silver halide color photosensitive material P having auxiliary tanks 2C, 2D, and 2E, and further having a drying unit 6 for drying the stabilized silver halide color photosensitive material P, and dried by the drying unit 6. To the external holder 9.

  The washing water or stabilizing solution container is a part of the first washing water or stabilizing solution container for first washing or stabilizing the bleach-fixed silver halide color photosensitive material P. 1st Stabilization Tank 1C and 1st Stabilization Auxiliary Tank 2C and Silver Halide Color Photosensitive Material P that has been washed or stabilized in the 1st Stabilization Tank 1C are then washed or stabilized for the second time. Next, the second stabilization tank 1D and the second stabilization auxiliary tank 2D, which are a part of the washing water or the stabilization liquid container, and the silver halide color photographic material P stabilized in the second stabilization tank 1D are as follows. And a third stabilization tank 1E and a third stabilization auxiliary tank 2E, which are a part of a third washing water or stabilization liquid container for washing or stabilizing treatment. Then, an overflow pipe (not shown) for sending the washing water or the stabilizing liquid exceeding the predetermined height to the second stabilization tank 1D is provided at a predetermined height of the third stabilization tank 1E. An overflow pipe (not shown) for sending the rinsing water or the stabilizing liquid over the first stabilizing tank 1C is provided at a predetermined height of the second stabilizing tank 1D, and the first stabilizing tank 1C, 2nd stabilization tank 1D and 3rd stabilization tank 1E are connected by the multistage countercurrent system. A liquid temperature detection tube and a heater linked to the liquid temperature detection tube are provided in each of the liquid tanks of the development processing section of the automatic processor 8 and in the color development tank and the bleach-fixing tank, and are controlled to a predetermined temperature. Yes.

In the present invention, it is preferable that the linear speed of conveyance of the automatic developing machine is 100 mm / second or less. More preferably, it is 20 mm / second-50 mm / second, Especially preferably, it is 25-45 mm / second. 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 that the float made of plastic or the like is floated on the liquid surface or covered with 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, the silver halide color light-sensitive material automatic developing machine having the above structure has a water replenishment tank, and silver ion elution means is provided in the water replenishment tank.

  As shown in FIG. 1B, the color developing tank 1A, the bleach-fixing tank 1B, the stabilizing tanks 1C, 1D, and 1E of the automatic processor 8 are fixed in order to compensate for the evaporation of water by continuous processing. There is provided a replenishing liquid supply device H provided with the silver ion elution means of the present invention for carrying out a quantity of replenishing liquid, and the replenishing liquid containing predetermined silver ions is supplied from the replenishing liquid supply device H for supplying the replenishing liquid. Replenishment is performed via the pipe 7 according to the evaporation amount.

  In the treatment method of the present invention, the replenisher supply device H provided with silver ion elution means has a silver elution cartridge constituted by a porous membrane carrying a hardly soluble silver compound, a silver elution cartridge constituted by silver impregnated activated carbon, A silver elution cartridge or an electrolytic silver ion elution device composed of silver-plated fibers is preferable.

  Moreover, in the processing method of this invention, adding the water replenisher containing the silver ion manufactured using the water replenisher supply apparatus provided with the silver ion elution means to any of the processing tank demonstrated in FIG. One feature and one preferred embodiment is to replenish the color developing tank with a replenishing solution containing silver ions produced by using a replenishing solution supplying apparatus having a silver ion eluting means. Conventionally, it has been studied as a means for preventing descaling in a color developing tank, but the antibacterial effect is not enough or it often affects the developability of the color developer, and it has not been put into practical use. By applying the replenishing solution supply apparatus provided with the silver ion eluting means of the present invention, it was possible to achieve a sufficient continuous antibacterial effect and a stable continuous process with little influence on developability. Further, in the processing method of the present invention, a replenishing solution containing silver ions produced using a replenishing solution supply device equipped with silver ion eluting means is replenished to the color developing tank, the bleach-fixing tank, the washing tank or the stabilizing tank. Is more preferable from the viewpoint of further achieving the object effect of the present invention.

  Next, a replenishing liquid supply apparatus provided with the silver ion elution means of the present invention will be described.

  The replenisher supply device of the present invention is not particularly limited as long as the silver ion concentration can be maintained at a desired concentration. In the present invention, the silver ion elution means carries 1) a hardly soluble silver compound. A silver elution cartridge composed of a porous membrane, 2) a silver elution cartridge composed of silver-impregnated activated carbon, 3) a silver elution cartridge composed of silver-plated fibers, or 4) an electrolytic silver ion elution device Is preferred.

  A silver elution cartridge composed of a porous membrane carrying a sparingly soluble silver compound that can be suitably used as a silver ion elution means in the replenisher supply device of the present invention will be described.

  The porous membrane referred to in the present invention is not limited as long as it can filter a fluid such as water. For example, a filter formed by winding a thread-like thread generally called a thread wound filter around a bobbin, or a water jet method. Examples thereof include nonwoven fabrics produced by needle punching, paper making, etc., and porous flat membranes and hollow fiber membranes produced by wet spinning, melt spinning and drawing. Further, the method of supporting the hardly soluble silver compound may be any method that does not cause the hardly soluble silver compound to fall off by passing water. For example, in the case of a nonwoven fabric produced by a papermaking method, it is difficult to use a slurry-like raw material. It is possible to support a sparingly soluble silver compound by dispersing paper and making paper, and also in the case of a porous flat membrane or hollow fiber membrane produced by a wet spinning method, a melt spinning drawing method, etc. A sparingly soluble silver compound can be supported by dispersing a sparingly soluble silver compound in a raw material to produce a porous film. In addition, a method of dispersing a sparingly soluble silver compound in a solution containing a binder and immersing and drying the porous film in the solution, or a method of generating a sparingly soluble silver compound by a chemical reaction on the surface of the porous film Etc. The pore diameter of the porous membrane is not particularly limited and can be appropriately set according to the application.

The poorly soluble silver compound in the present invention refers to a silver compound that is difficult to dissolve in a fluid such as water, and a preferred example is silver sulfide. For example, silver sulfide has a solubility in water of 6.15 × 10 ⁻¹³ g / L (25 ° C.) and is almost insoluble in water. Therefore, silver sulfide hardly elutes only by contact with a fluid such as water, but elutes only when it comes into contact with a fluid such as water containing an acid or an oxidizing agent. In addition, silver chloride, silver bromide, silver iodide, etc. can be used, but when they stay in water for a long time, they dissolve at a high concentration regardless of the presence or absence of an oxidizing agent such as hypochlorous acid. Therefore, it is preferable to use silver sulfide as the hardly soluble silver compound.

  Examples of the acid or oxidizing agent in the present invention include nitric acid, hydrochloric acid, sulfuric acid, hypochlorous acid, aqueous hydrogen peroxide, and the like. In consideration of danger, reactivity, etc., hypochlorous acid is used. It is preferable to use it.

  In the silver elution method of the present invention, it is necessary to appropriately add an acid or an oxidizing agent in water before contacting the poorly soluble silver compound in order to elute silver, but hypochlorous acid is added in advance for antibacterial activity. It is not necessary to add an acid or an oxidizing agent again when silver is eluted in the existing tap water. In this case, hypochlorous acid is decomposed with the elution of silver, so the smell of hypochlorous acid and skin irritation can be reduced or eliminated.

  Specific means of the silver elution cartridge composed of the porous film supporting the hardly soluble silver compound according to the present invention is described in, for example, Japanese Patent Application Laid-Open Nos. 2001-25772 and 2001-25773. A method can be mentioned.

  Next, a silver elution cartridge composed of silver-impregnated activated carbon that can be suitably used as a silver ion elution means in the replenisher supply device of the present invention will be described.

  The silver-impregnated activated carbon according to the present invention is not harmful to the activated carbon having a porous structure produced from plant raw materials and the like, and is insoluble with inorganic salts of sparingly soluble silver, for example, silver chloride, silver bromide, silver iodide, oxidized Silver salts such as silver and silver sulfide were added. As this attachment method, only a single salt may be added, a mixed salt may be added, or different types of salts may be added in layers.

  The elution concentration of silver ions can be controlled by the solubility of the inorganic silver salt, the surface area of the activated carbon, and the contact speed with water.

  With respect to the details of the silver elution cartridge constituted by the silver-impregnated activated carbon according to the present invention and the specific structure of the silver elution cartridge to be used, for example, the method described in JP-A-10-314754 can be mentioned. .

  Next, a silver elution cartridge composed of silver-plated fibers that can be suitably used as silver ion elution means in the replenisher supply device of the present invention will be described.

  In the silver-plated fibers according to the present invention, natural fibers, synthetic fibers, and inorganic fibers are used as the fiber material for silver plating. Examples of natural fibers include cotton, hemp, regenerated cellulose, and the like. As such, each fiber such as polyamide, acrylic, polyolefin (for example, polyethylene), polyester, aramid, polyurethane, vinyl chloride, carbon fiber and the like is used. Examples of inorganic fibers include wollastonite and asbestos. These natural fibers, synthetic fibers, and inorganic fibers may be used alone or in combination of two or more. These natural fibers, synthetic fibers, and inorganic fibers may be mixed and used. The thickness of these fibers is 0.1 to 15d (d = denier). If the thickness is smaller than 0.1d, a large amount of metal coating is required and the specific gravity increases, and spinning becomes difficult. And the antibacterial or bactericidal effect cannot be fully exhibited.

  Even if the filter member used for this invention consists only of silver plating fiber, you may mix a non-silver plating fiber with this. Moreover, the thread | yarn, string, nonwoven fabric, cloth, and net-like body which consist only of silver plating fiber may be formed, and non silver plating fiber may be combined with these. When it has this non-silver plating fiber, the content is 70 mass parts or less with respect to silver plating fiber, Preferably it is 50 mass parts or less. When the content of the non-silver plated fiber exceeds 70 parts by mass, the antibacterial and bactericidal properties become insufficient for the purification effect. Further, the mixed form of the non-silver plated fibers will be described. (B) Spinning with a fiber obtained by mixing silver-plated fibers and non-silver-plated fibers to form a yarn or a non-woven fabric. Either use yarn to form a string, or form yarn by spinning yarn consisting only of silver-plated fibers and yarn consisting only of non-silver plated fibers, or (c) using these yarns There are any modes of forming a cloth, a net or the like.

When silver-plated fiber and non-silver-plated fiber are mixed in advance, an amount that does not lose the antibacterial or bactericidal action can be mixed. It can be adjusted by changing it to 1 to 100 g per 1 m ^{2 of the} nonwoven fabric. Preferably it is 1-50 g / m < ² >. Silver amount can not be obtained but a sufficiently satisfactory effect of the antimicrobial to the bactericidal action is less than the nonwoven fabric 1 m ² per 1 g / m ^2, also the amount of silver no effect as the fiber is more than the nonwoven fabric 1 m ² per 100 g / m ² Fiber processing is not possible.

  Methods for plating silver on the fiber include an electroless plating method and a vacuum deposition method, but the electroless plating method is excellent in mass productivity. The silver amount with respect to the silver plating fiber used by this invention is 1-50 mass% (silver mass / silver plating fiber mass), Preferably it is 1-30 mass%. If the silver plating amount is less than 1% by mass, the fiber cannot be sufficiently coated with silver and the antibacterial or bactericidal action is not satisfactory, and if it exceeds 50% by mass, the flexibility is reduced and the effect as a fiber is obtained. There is no fiber processing.

  The electroless plating method is a method in which metal is deposited on the surface of the object by immersing the object in a solution in which the metal is dissolved as an ion or complex and dropping a reducing agent (published by Ebara store, field technician). Pp. 505 to 524 of Practical Plating for Metal (I), see the Japan Plating Association edition), and the vacuum vapor deposition method is a method of making a gas (vapor) by heating a metal in a vacuum. This is a method of coating by precipitating on an object to be treated, and this is a generally known plating method.

  Next, an electrolytic silver ion elution device that can be suitably used as a silver ion elution means in the replenisher supply device of the present invention will be described.

  The electrolytic silver ion elution apparatus according to the present invention is an apparatus that can electrolyze using a silver electrode and continuously supply the eluted silver ions at a low concentration. Specifically, raw water is supplied to the first electrolytic cell. Electrolysis is performed by introducing the anode chamber and the cathode chamber. First, alkaline ionized water flowing out from the cathode chamber of the first electrolytic cell is introduced into the second electrolytic cell for electrolysis, and the second electrolytic cell is provided with silver at the anode, and silver is ionized and eluted by electrolysis. To do. The electrolysis in the second electrolytic cell is preferably performed under conditions of a voltage of 10 to 100 V, a current of 20 to 450 mA, and a flow rate of 4 to 6 L / min. The elution amount of silver increases as the electrolysis current increases. However, the silver ionized and eluted reacts with chlorine ions in the raw water and colloids. It is only a part.

  In the present invention, it is preferable to set the conditions of the silver ion elution means such that the silver ion concentration of the replenishing liquid replenished to the automatic processor is 10 ppb or more and 1000 ppb or less, and the silver ion concentration is lower than 10 ppb. In some cases, for example, even if 70% or more is ionized, the bactericidal effect is insufficient, and when the silver ion concentration exceeds 1000 ppb, it is preferable to avoid from the viewpoint of safety. The silver ion concentration here can be measured using, for example, atomic absorption spectrophotometry.

  In the processing method of the present invention, the amount of water replenished to each processing tank includes the structure of an automatic processor (for example, the opening ratio of the processing tank), processing conditions (for example, processing temperature, replenishment amount of processing liquid), and automatic development. Since it is difficult to define in general according to the environmental conditions and operating conditions of operating the machine, the replenishing liquid having a silver ion concentration of 10 ppb or more and 1000 ppb or less depending on the amount of water reduced by evaporation or the like depending on the operating conditions Is added as appropriate.

Next, details of each processing solution used in the processing method of the present invention will be described.
First, components of the color developer used in the color development process according to the present invention will be described.

  Preferred examples of the color developing agent are 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-Methanesulfonamidoethyl) aniline 9) 4-Amino-N, N-diethyl-3- (β-hydroxyethyl) aniline 10) 4-Amino-3-methyl-N-ethyl-N- (β- Me Xylethyl) 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 14) N- (4-amino-3-methylphenyl) -3-hydroxypyrrolidine 15) N- (4-Amino-3-methylphenyl) -3- (hydroxymethyl) pyrrolidine 16) N- (4-Amino-3-methylphenyl) -3-pyrrolidinecarboxamide Of the above p-phenylenediamine derivatives, particularly preferred examples Compounds 5), 6), 7), 8) and 12), among which 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 agent 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, per liter of the developing solution. 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 developer preservative like sulfite ion, but at the same time hydroxylamine itself Since the silver developing activity of the toner may affect the photographic characteristics, it is necessary to keep this addition amount small.

  In addition to 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 to prevent air oxidation of the color developing agent. Among them, 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- No. 143,020, Japanese Patent Publication No. 48-30696, and the like.

  Other preservatives include various metals described in JP-A-57-44148 and 57-53749, salicylic acids described in JP-A-59-180588, and JP-A-54-3532. Containing the alkanolamines described, polyethyleneimines described in JP-A-56-94349, aromatic polyhydroxy compounds described in US Pat. No. 3,746,544, etc. Also good. 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-1-97953, 1-186939, 1-186940, 1-187557, and the like. In particular, adding both a hydroxylamine derivative and amines may be effective in terms of improving the stability of the color developer and improving stability during continuous processing. Examples of the amines include cyclic amines described in JP-A-63-239447, amines described in JP-A-63-128340, and other JP-A-1-186939. Examples thereof include amines described in JP-A-1-187557. The content of the preservative in the processing agent varies depending on the type of the preservative, but generally the concentration in the working solution is 1 to 200 mmol, preferably 10 to 100 mmol per liter of the developer. Added.

Chlorine ions may be added to the color developer as necessary. A color developer usually contains chlorine ions of 3.5 × 10 ^{−2 to} 1.5 × 10 ⁻¹ mol / liter in many cases, but chlorine ions are usually released to the developer as a by-product of development. Therefore, it is often unnecessary to add to the replenishment developer.

With respect to bromine ions, the bromine ions in the color developer are preferably 1.0 × 10 ⁻³ mol / liter or less. However, it is often not necessary for the color developer to be the same as the above-mentioned chlorine ions, but when added, bromine ions are added to the processing agent as necessary so that the bromine ion concentration is in the above range. There is also.

  In the present invention, when a halide is used as an additive component in a color developer or developer replenisher, sodium chloride, potassium chloride, ammonium chloride, lithium chloride, nickel chloride, magnesium chloride, manganese chloride and manganese chloride are used as the chloride ion supplying substance. Among them, calcium is preferable, and sodium chloride and potassium chloride are preferable. 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 color developer is preferably added so that the pH of the color developer is 9.0 to 13.5 and the pH of the replenisher is 9.0 to 13.5. May contain an alkali agent, a buffering agent and, if necessary, an acid agent so that the pH value can be maintained.

  In order to maintain the pH when the color developer is prepared, various buffers are preferably used. 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. Carbonate, phosphate, tetraborate, and hydroxybenzoate are particularly excellent in buffering ability in a high pH range of pH 9.0 or higher, and even when added to a color developer, they adversely affect photographic performance (fogging). It is particularly preferable to use these buffering agents.

  As the other color developing composition, for example, various chelating agents that are calcium or magnesium precipitation inhibitors or color developer stability improvers can be added to the color developer of the present invention. 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 optional development accelerator can be added to the color developer of the present invention. Examples of the development accelerator include 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. Or the thioether compounds described in the specification, p-phenylenediamine compounds described in JP-A-52-49829 and JP-A-50-15554, JP-A-50-137726, JP-B-44- No. 30074, quaternary ammonium salts described in JP-A-56-156826 and JP-A-52-43429, U.S. Pat. Nos. 2,494,903, 3,128,182, and 4,230. No. 3,796, No. 3,253,919, Japanese Examined Patent Publication No. 41-11431, U.S. Pat. Nos. 2,482,546, 2,596,926 and 3,582. 346 and the like, 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, and JP-A-42-23883. Polyalkylene oxide, other 1-phenyl-3-pyrazolidones or imidazoles described in each publication or specification such as US Pat. No. 3,532,501 or the like can be added as necessary. The added amount in the composition is such that the concentration thereof is 0.001 to 0.2 mol, preferably 0.01 to 0.05 mol, per liter for both the color developer and replenisher prepared from the processing agent. It is decided.

  An optional antifoggant can be added to the color developer according to the present invention, if necessary, in addition to the halogen ions. 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. In addition, 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 added amount in the composition is determined so that the concentration thereof is 0.0001 to 0.2 mol, preferably 0.001 to 0.05 mol, per liter for both the developer and replenisher prepared from the processing agent. It is done.

  In the present invention, 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, and among the compounds described therein, Blankophor BSU liq. And Hakkol BRK.

  Next, the bleach-fixing solution used in the bleach-fixing step in the processing method of the present invention will be described.

  As a bleaching agent used in the bleach-fixing solution, a known bleaching agent can be used. In particular, an organic complex salt of iron (III) (for example, a complex salt of aminopolycarboxylic acids) or an organic compound such as citric acid, tartaric acid, malic acid or the like. Acid, persulfate, hydrogen peroxide and the like are preferable.

  Of these, an organic complex salt of iron (III) is particularly preferable from the viewpoint of rapid processing and prevention of environmental pollution. Aminopolycarboxylic acid useful for forming an organic complex salt of iron (III), or a salt thereof includes biodegradable ethylenediamine disuccinic acid (SS form), N- (2-carboxylate ethyl) -L-aspartic acid, beta-alanine diacetic acid, methyliminodiacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, 1,3-diaminopropanetetraacetic acid, propylenediaminetetraacetic acid, nitrilotriacetic acid, cyclohexanediaminetetraacetic acid, iminodiacetic acid And glycol ether diamine tetraacetic 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, methylimino Diacetic acid is preferred because its iron (III) complex salt has good photographic properties. These ferric ion 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 a ferric ion complex salt in a solution. Moreover, you may use a chelating agent in excess rather than forming a ferric ion complex salt. Of the iron complexes, aminopolycarboxylic acid iron complexes are preferred.

  The amount of the bleaching agent added is such that the concentration of the prepared treatment liquid is 0.01 to 1.0 mol / liter, preferably 0.03 to 0.80 mol / liter, more preferably 0.05 to 0.70 mol / liter. Liter, more preferably 0.07 to 0.50 mol / liter.

  A bromide compound is preferably added to the bleach-fixing solution from the viewpoint of further exerting the object effect of the present invention. For example, potassium bromide, ammonium bromide and the like can be applied.

  In addition, various known organic acids (for example, glycolic acid, succinic acid, maleic acid, malonic acid, citric acid, sulfosuccinic acid, etc.), organic bases (for example, imidazole, dimethylimidazole, etc.) , 2-picolinic acid and other compounds represented by the general formula (Aa) described in JP-A-9-211819, and kojic acid and other general formulas (Bb) It is preferable to contain the compound represented by these. The amount of these compounds added is determined so that the concentration of the prepared treatment solution is preferably 0.005 to 3.0 mol, more preferably 0.05 to 1.5 mol per liter.

  Next, the fixing agent will be described.

  Fixing agents used in these bleach-fixing agents are known fixing chemicals, that is, thiosulfates such as sodium thiosulfate and ammonium thiosulfate, thiocyanates such as sodium thiocyanate and ammonium thiocyanate, ethylenebisthioglycolic acid, These are water-soluble silver halide solubilizers such as thioether compounds such as 3,6-dithia-1,8-octanediol and thioureas, and these can be used alone or in combination. 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 chemical in the fixing solution and the bleach-fixing solution prepared from the granular type processing agent is preferably 0.3 to 3 mol, more preferably 0.5 to 2.0 mol, per liter of the prepared solution. .

  In the present invention, the dissolution pH range of the bleach-fixing agent 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. The pH range of the bleaching solution made from the granule of the present invention is 8 or less, preferably 2 to 7, and particularly preferably 2 to 6. If the pH is lower than this, the deterioration of the liquid and the leuco conversion of the cyan dye are promoted. Conversely, if the pH is higher than this, desilvering is delayed and stain is likely to occur. In order to adjust the pH, the solid acid described above and the solid alkali potassium hydroxide, sodium hydroxide, lithium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate and acidic or alkaline as necessary are used. Buffering agents and the like can be added.

  Further, the bleach-fixing agent can contain various other fluorescent whitening agents, antifoaming agents, surfactants, polyvinylpyrrolidone and the like. The fluorescent brightening agent can also be included in the color developer so that its concentration is 0.02 to 1.0 mol / liter. Bleach fixing agents and fixing agents are preservatives such as sulfites (for example, sodium sulfite, potassium sulfite, ammonium sulfite), bisulfites (for example, ammonium bisulfite, sodium bisulfite, potassium bisulfite), It preferably contains a sulfite ion releasing compound such as a sulfite (eg, potassium metabisulfite, sodium metabisulfite, ammonium metabisulfite, etc.). These compounds are preferably contained in an amount of about 0.02 to 1.0 mol / liter in terms of sulfite ion.

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

  After the bleach-fixing is completed, a washing process and a stabilization process for stabilizing the image are performed.

  It is particularly preferred for the purposes of the present invention that the stabilizing solution contains a chelating agent having a chelate stability constant for iron ions of 8 or more. Here, the chelate stability constant is L.I. G. Sillen, A.M. E. "Stability Constants of Metal-ion Complexes" by Martell, The Chemical Society, London (1964), S.M. Chaberek, A .; E. This means a constant generally known by Martell's “Organic Sequencing Agents” Wiley (1959).

Examples of the chelating agent having a chelate stability constant for iron ions of 8 or more include organic carboxylic acid chelating agents, organic phosphoric acid chelating agents, inorganic phosphoric acid chelating agents, and polyhydroxy compounds. The iron ion means ferric ion (Fe ³⁺ ).

  Specific examples of the chelating agent having a chelate stability constant with ferric ion of 8 or more include the following compounds, but are not limited thereto. That is, ethylenediaminediorthydroxyphenylacetic acid, diaminopropanetetraacetic acid, nitrilotriacetic acid, hydroxyethylenediaminetriacetic acid, dihydroxyethylglycine, ethylenediaminediacetic acid, ethylenediaminedipropionic acid, iminodiacetic acid, diethylenetriaminepentaacetic acid, hydroxyethyliminodiacetic acid, Diaminopropanoltetraacetic acid, transcyclohexanediaminetetraacetic acid, glycol etherdiaminetetraacetic acid, ethylenediaminetetrakismethylenephosphonic acid, nitrilotrimethylenephosphonic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, 1,1-diphosphonoethane-2-carboxylic acid 2-phosphonobutane-1,2,4-tricarboxylic acid, 1-hydroxy-1-phosphonopropane-1,2,3-tricarboxylic acid, Examples include techol-3,5-diphosphonic acid, sodium pyrophosphate, sodium tetrapolyphosphate, and sodium hexametaphosphate, particularly preferably diethylenetriaminepentaacetic acid, nitrilotriacetic acid, nitrilotrimethylenephosphonic acid, 1-hydroxyethylidene-1,1. -Diphosphonic acid, etc. Among them, 1-hydroxyethylidene-1,1-diphosphonic acid is most preferably used.

  The amount of the chelating agent used is preferably 0.01 to 50 g per liter of the stabilizing solution, more preferably 0.05 to 20 g.

  Moreover, an ammonium compound is mentioned as a preferable compound added to a stabilization liquid. These are supplied by various inorganic and organic ammonium salts, specifically ammonium hydroxide, ammonium bromide, ammonium carbonate, ammonium chloride, ammonium hypophosphite, ammonium phosphate, ammonium phosphite, fluoride. Ammonium fluoride, ammonium acid fluoride, ammonium fluoroborate, ammonium arsenate, ammonium hydrogen carbonate, ammonium hydrogen fluoride, ammonium hydrogen sulfate, ammonium sulfate, ammonium iodide, ammonium nitrate, ammonium pentaborate, ammonium acetate, ammonium adipate, laurin Ammonium tricarboxylate, ammonium benzoate, ammonium carbamate, ammonium citrate, ammonium diethyldithiocarbamate, ammonium formate, malic acid water Ammonium, ammonium hydrogen oxalate, ammonium hydrogen phthalate, ammonium hydrogen tartrate, ammonium thiosulfate, ammonium sulfite, ethylenediaminetetraacetic acid ammonium, ethylenediaminetetraacetic acid ferric ammonium, ammonium lactate, ammonium malate, ammonium maleate, ammonium oxalate, Ammonium phthalate, ammonium picrate, ammonium pyrrolidine dithiocarbamate, ammonium salicylate, ammonium succinate, ammonium sulfanilate, ammonium tartrate, ammonium thioglycolate, 2,4,6-trinitrophenol ammonium and the like. These may be used alone or in combination of two or more. The addition amount of the ammonium compound is preferably in the range of 0.001 mol to 1.0 mol, and more preferably in the range of 0.002 to 0.8 mol, per liter of the stabilizing solution.

Furthermore, it is preferable to contain a sulfite in the stabilizing solution. The sulfite may be any organic or inorganic substance as long as it releases sulfite ions, but is preferably an inorganic salt. Preferred specific compounds include sodium sulfite, potassium sulfite, ammonium sulfite, ammonium bisulfite, potassium bisulfite, sodium bisulfite, sodium metabisulfite, potassium metabisulfite, ammonium metabisulfite and hydrosulfite. The sulfite is preferably added to the stabilizing solution in an amount of at least 1 × 10 ⁻³ mol / liter, more preferably 5 × 10 ⁻³ mol / liter to 10 ⁻¹ mol / liter. Is added, and is particularly effective for preventing stains. As an addition method, it may be added directly to the stabilizing solution, but it is preferably added to the stable replenishing solution.

  Other compounds that can be added to generally known stabilizing solutions include polyvinylpyrrolidone (PVP K-15, K-30, K-90), organic acid salts (citric acid, acetic acid, succinic acid, oxalic acid, Benzoic acid, etc.), pH adjusters (phosphate, borate, hydrochloric acid, sulfuric acid, etc.), fungicides (phenol derivatives, catechol derivatives, imidazole derivatives, triazole derivatives, siabendazole derivatives, organic halogen compounds, other papers) -Antifungal agent known as a slime control agent in the pulp industry) or optical brighteners, surfactants, preservatives, metal salts such as Bi, Mg, Zn, Ni, Al, Sn, Ti, Zr, etc. There is. One or more of these compounds can be selected and used as long as the effects of the present invention are not impaired.

  After the stabilization treatment, no water washing treatment is required, but rinsing by a small amount of water washing in a very short time, surface washing, etc. can be optionally performed.

The presence of a soluble iron salt in the stabilizing solution is preferable for achieving the effects of the present invention. The soluble iron salt is preferably used in the stabilizing solution at a concentration of at least 5 × 10 ⁻³ mol / liter, more preferably in the range of 8 × 10 ⁻³ to 15 × 10 ⁻² mol / liter, even more preferably. Is in the range of 12 × 10 ⁻³ to 10 × 10 ⁻² mol / liter. These soluble iron salts may be added to the stabilizing solution (tank solution) by adding them to the stabilizing solution replenishing solution, or may be added to the stabilizing solution (tank solution) by elution from the photosensitive material in the stabilizing solution. It may be added to the tank solution), or may be added to the stabilizing solution (tank solution) by adhering to the photosensitive material to be processed from the previous bath.

  In the present invention, a stabilizing solution in which calcium ions and magnesium ions are reduced to 5 ppm or less by performing an ion exchange resin treatment may be used, and a method of further containing the above antibacterial agent or halogen ion releasing compound. May be used.

  In the present invention, the pH of the stabilizing solution is preferably in the range of 5.5 to 10.0. The pH adjuster that can be contained in the stabilizing solution may be any of commonly known alkali agents or acid agents.

    The replenishment amount of the stabilizing solution is preferably from 0.1 to 50 times the amount of the pre-bath (bleach-fixing solution) brought in per unit area of the light-sensitive material from the viewpoint of rapid processability and dye image storage, and particularly 0.5 to 30 times. Double is preferred.

  In the present invention, the washing or stabilizing solution may contain an additive such as a known anti-scale agent, antifungal agent, or preservative in addition to the sulfite. Examples of compounds having these effects include orthophenylphenol, benzoisothiazolin-3-one, 2,2-dibromo-2-nitroethanol, 2-bromo-2-nitro-1,3-propanediol, and 8-hydroxy. Examples include quinoline, hexahydro-1,3,5-tris (2-hydroxyethyl) -s-triazine, 2,4-dichloro-S-hydroxytriazine sodium. Particularly preferred are orthophenylphenol, 2-bromo-2-nitro-1,3-propanediol, 2,4-dichloro-S-hydroxytriazine sodium and the like.

  In the treatment process of the stabilization tank, it is preferable to replenish each tank individually to become waste liquid, but it is not effective in reducing the replenishment amount. Therefore, it is preferable to use a so-called counter current method in which the replenisher enters the last tank, sequentially overflows to the previous tank, and overflows from the front tank as waste liquid.

In the processing method of the present invention, when the silver halide color light-sensitive material to be processed is a silver halide color light-sensitive material having a transparent support, the processing temperature is generally 30 to 40 ° C. In rapid processing, it is 38-65 degreeC, Preferably it is 40-55 degreeC. The development processing time is 1 to 8 minutes in general processing, but 15 to 195 seconds in rapid processing, and preferably 20 to 150 seconds. The replenishment amount is 600 ml per 1 m ² of the photosensitive material, but is 30 to 390 ml, preferably 50 to 300 ml, and more preferably 80 to 200 ml in the low replenishment processing. In the case where the silver halide color light-sensitive material to be developed is a silver halide color light-sensitive material having a reflective support, the processing temperature is generally 30 to 40 ° C., but 38 to 65 ° C. for rapid processing. It is. The development processing time is 30 seconds to 3 minutes in general processing, but 5 to 45 seconds in rapid processing, and preferably 5 to 20 seconds. The replenishment amount is 161 ml per 1 m ² of the photosensitive material, but is 10 to 150 ml, preferably 20 to 100 ml, more preferably 25 to 80 ml in the low replenishment processing.

In color development processing, the color development step is followed by a bleach-fixing step, where processing with a bleach-fixing solution is performed. The bleach-fixing process according to the present invention has a processing time of 5 to 240 seconds, preferably 10 to 60 seconds. The treatment temperature is 25 ° C to 60 ° C, preferably 30 ° C to 50 ° C. The replenishment amount is 10 ml to 250 ml, preferably 10 ml to 100 ml, particularly preferably 15 ml to 60 ml per 1 m ² of the light-sensitive material.

  The amount of washing water in the washing step can be set in a wide range depending on the characteristics of the photosensitive material (for example, depending on the material used such as a coupler) and application, the washing water temperature, the number of washing tanks (number of stages), and various other conditions. Of these, the relationship between the number of flushing tanks and the amount of water in the multi-stage countercurrent method is the Journal of the Society of Motion Picture and Television Engineers, 64th (JOURNAL OF THE SOCIETY OF MOTION PICTURE TELEVISION ENGINEERS). Volume, p. 248-253 (May 1955 issue). 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 method, the amount of water to be washed 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 stable bath containing an antibacterial and antifungal agent as described above is preferable.

  The preferred pH of the water washing step or stabilization step is 4 to 10, more preferably 5 to 8. The temperature can be variously set depending on the use and characteristics of the photosensitive material, but is generally 20 ° C to 50 ° C, preferably 25 ° C to 45 ° C. Drying is performed following the water washing and / or stabilization step. From the viewpoint of reducing the amount of moisture brought into the image film, drying can be accelerated by absorbing water with a squeeze roller or cloth immediately after leaving the washing bath. As a matter of course as an improvement means from the dryer side, 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.

  Next, details of the silver halide color light-sensitive material which is developed by the processing method of the present invention will be described.

  The silver halide color photographic light-sensitive material according to the present invention mainly comprises a yellow dye-forming coupler-containing blue-sensitive silver halide emulsion layer, a magenta dye-forming coupler-containing green light-sensitive silver halide emulsion layer on a support. It has a photographic constituent layer comprising at least one each of a red-sensitive silver halide emulsion layer containing a cyan dye-forming coupler and a non-photosensitive hydrophilic colloid layer. The silver halide emulsion layer containing the yellow dye-forming coupler is used as a yellow coloring layer, the silver halide emulsion layer containing the magenta dye-forming coupler is used as a magenta coloring layer, and the silver halide containing the cyan dye-forming coupler. The emulsion layer functions as a cyan coloring layer. The silver halide emulsions contained in the yellow coloring layer, the magenta coloring layer and the cyan coloring layer, respectively, are sensitive to light in different wavelength regions (for example, light in the blue region, green region and red region). It is preferable to have. In addition to the yellow coloring layer, the magenta coloring layer, and the cyan coloring layer, the photosensitive material may have an antihalation layer, an intermediate layer, and a colored layer as a non-photosensitive hydrophilic colloid layer to be described later if desired.

  Details of the components of the silver halide color photographic material will be described below.

  The silver halide emulsion used in the present invention is preferably a silver halide emulsion comprising 95 mol% or more of silver chloride, and any halogen such as silver chloride, silver chlorobromide, silver chloroiodobromide, silver chloroiodide, etc. What has a composition is used. Among them, a silver chlorobromide containing 95 mol% or more of silver chloride, a silver halide emulsion having a portion containing a high concentration of silver bromide is particularly preferably used, and 0.05% of silver iodide is present in the vicinity of the surface. Silver chloroiodide containing ˜0.5 mol% is also preferably used. Of the silver halide emulsion having a silver bromide-rich portion, the silver bromide-containing portion may be a so-called core-shell emulsion, or simply forming a complete layer without forming a complete layer. A so-called epitaxy-bonded region in which only a region having a partially different composition exists may be formed. The portion where silver bromide is present at a high concentration is particularly preferably formed at the apex of the crystal grain on the surface of the silver halide grain. Further, the composition may change continuously or discontinuously.

It is advantageous that the negative silver halide emulsion used in the present invention contains heavy metal ions. This is expected to improve so-called reciprocity failure and prevent desensitization in high-illuminance exposure and prevent softening on the shadow side. Heavy metal ions that can be used for such purposes include Group 8-10 metals such as iron, iridium, platinum, palladium, nickel, rhodium, osmium, ruthenium, and cobalt, and group 12 metals such as cadmium, zinc, and mercury. Group transition metals and ions of lead, rhenium, molybdenum, tungsten, gallium, and chromium can be given. Of these, metal ions of iron, iridium, platinum, ruthenium, gallium and osmium are preferable. These metal ions can be added to the silver halide emulsion in the form of a salt or a complex salt. When the heavy metal ion forms a complex, as its ligand, cyanide ion, thiocyanate ion, cyanate ion, chloride ion, bromide ion, iodide ion, carbonyl, nitrosyl, ammonia, water, pyridine, Pyrrol, pyrazole, imidazole, thiazole, 1,2,4-triazole, 2,2′-biimidazole, 2,2′-bipyridine or 2,2 ′: 6 ′, 2 ″ -terpyridine compound is preferably used. Cyanide ion, chloride ion, bromide ion, water, nitrosyl, 5-methylthiazole, 1,2,4-triazole, etc. In order to contain a heavy metal ion in a silver halide emulsion, the heavy metal compound is added. Before formation of silver halide grains, during formation of silver halide grains, after formation of silver halide grains In order to obtain a silver halide emulsion satisfying the above-described conditions, the heavy metal compound is dissolved together with the halide salt to completely or partly form the grain. In addition, it is also possible to prepare silver halide fine particles containing these heavy metal compounds in advance and then add the heavy metal ions to the silver halide. The amount added to the emulsion is preferably 1 × 10 ⁻⁹ mol or more and 1 × 10 ⁻² mol or less, and more preferably 1 × 10 ⁻⁸ mol or more and 5 × 10 ⁻⁵ mol or less per mol of silver halide. preferable.

  Any particle shape can be used in the present invention. One preferable example is a cube having a (100) plane as a crystal surface. Also, U.S. Pat. Nos. 4,183,756, 4,225,666, JP-A-55-26589, JP-B-55-42737, The Journal of Photographic Science (J. Photogr. Sci.) No. 21, page 39 (1973), etc., can be used to produce particles having a shape such as octahedron, tetrahedron, dodecahedron, etc. . Furthermore, particles having twin planes may be used.

  The grains used in the present invention are preferably grains having a single shape, but it is particularly preferred that two or more monodispersed silver halide emulsions are added to the same layer.

  The particle size of the particles used in the present invention is not particularly limited, but is preferably 0.1 to 1.2 μm, more preferably 0.2 when considering other photographic performances such as rapid processability and sensitivity. It is the range of -1.0 micrometer.

  This particle size can be measured using the projected area or diameter approximation of the particle. If the particles are substantially uniform in shape, the particle size distribution can be expressed fairly accurately as a diameter or projected area.

  The grain size distribution of the silver halide grains used in the present invention is preferably monodispersed silver halide grains having a coefficient of variation of 0.22 or less, more preferably 0.15 or less, and particularly preferably a coefficient of variation of 0.1. Two or more monodispersed emulsions of 15 or less are added to the same layer. Here, the variation coefficient is a coefficient representing the breadth of the particle size distribution, and is defined by the following equation.

Coefficient of variation = S / R
(Here, S represents the standard deviation of the particle size distribution, and R represents the average particle size.)
As a silver halide emulsion preparation apparatus and method, various methods known in the art can be used.

  The emulsion used in the present invention may be obtained by any of the acidic method, neutral method and ammonia method. The particles may be grown at one time, or may be grown after the seed particles are made. The method for making seed particles and the method for growing them may be the same or different.

  Further, the form of reacting the soluble silver salt and the soluble halide salt may be any of a forward mixing method, a back mixing method, a simultaneous mixing method, a combination thereof, and the like, but those obtained by the simultaneous mixing method are preferred. Furthermore, the pAg controlled double jet method described in JP-A No. 54-48521 can be used as one type of the simultaneous mixing method.

  Further, an apparatus for supplying a water-soluble silver salt solution and a water-soluble halide salt aqueous solution from an addition device arranged in a reaction mother liquor described in JP-A-57-92523 and JP-A-57-92524, German Published Patent No. 2921164 An apparatus for continuously adding a water-soluble silver salt solution and a water-soluble halide salt aqueous solution described in JP-A No. 56-501776, etc. An apparatus that forms grains while maintaining the distance between silver halide grains constant by concentration by a method may be used.

  Further, if necessary, a silver halide solvent such as thioether may be used. Further, a compound having a mercapto group, a nitrogen-containing heterocyclic compound, or a compound such as a sensitizing dye may be added at the time of forming silver halide grains or after the completion of grain formation.

  The negative silver halide emulsion used in the present invention can be used in combination of a sensitizing method using a gold compound and a sensitizing method using a chalcogen sensitizer. As the chalcogen sensitizer, a sulfur sensitizer, a selenium sensitizer, a tellurium sensitizer and the like can be used, and a sulfur sensitizer is preferable. Examples of the sulfur sensitizer include thiosulfate, triethylthiourea, allylthiocarbamide thiourea, allyl isothiocyanate, cystine, p-toluenethiosulfonate, rhodanine, inorganic sulfur and the like.

The amount of the sulfur sensitizer, it is preferred to vary the size, etc. of the effect of the type of silver halide emulsions applied or expectations, per mol of silver halide 5 × 10 ^-10 ~5 × 10 ^- A range of ⁵ mol, preferably 5 × 10 ^{−8 to} 3 × 10 ⁻⁵ mol is preferable.

As the gold sensitizer, various gold complexes such as chloroauric acid and gold sulfide can be added. Examples of the ligand compound used include dimethyl rhodanine, thiocyanic acid, mercaptotetrazole, mercaptotriazole and the like. The amount of gold compound used is not uniform depending on the type of silver halide emulsion, the type of compound used, ripening conditions, etc., but usually 1 × 10 ⁻⁴ mol to 1 × 10 ⁻⁸ per mol of silver halide. Mole is preferred. More preferably 1 × 10 ^-5 mol to 1 × 10 ^-8 mol.

  As a chemical sensitization method for the negative silver halide emulsion used in the present invention, a reduction sensitization method may be used.

  The silver halide color light-sensitive material according to the present invention has a layer containing a silver halide emulsion spectrally sensitized in a specific region of a wavelength region of 400 to 900 nm. The silver halide emulsion contains one or a combination of two or more sensitizing dyes.

  As the spectral sensitizing dye used in the silver halide emulsion used in the present invention, any known compound can be used. As the blue-sensitive sensitizing dye, it is described in JP-A-3-251840, page 28. BS-1 to 8 can be preferably used alone or in combination. As the green photosensitive sensitizing dye, GS-1 to 5 described on page 28 of the same publication are preferably used. As the red photosensitive sensitizing dye, RS-1 to 8 described in page 29 of the same publication are preferably used.

  These sensitizing dyes may be added at any time from the formation of silver halide grains to the end of chemical sensitization. In addition, these dyes may be added as a solution by dissolving in water or an organic solvent miscible with water such as methanol, ethanol, fluorinated alcohol, acetone, dimethylformamide, or a sensitizing dye. May be added as a water miscible solvent solution, emulsion or suspension having a density greater than 1.0 g / ml.

As a method for dispersing the sensitizing dye, in addition to a method of mechanically pulverizing and dispersing fine particles having a size of 1 μm or less in an aqueous system using a high-speed stirring type disperser, a pH of 6 to 5 as described in JP-A No. 58-105141 can be used. 8. A method of mechanically pulverizing and dispersing fine particles having a size of 1 μm or less in an aqueous system under conditions of 60 to 80 ° C., and a surface tension described in JP-B-60-6496 of 3.8 × 10 ⁻² N / m or less A method of dispersing in the presence of a surfactant that suppresses to a minimum, dissolved in an acid that does not substantially contain water and that does not exceed pKa as described in JP-A-50-80826, and adds the solution to an aqueous solution A method of dispersing and adding this dispersion to a silver halide emulsion can be used.

  The dispersion medium used for dispersion is preferably water, but a small amount of an organic solvent can be added to adjust the solubility, or a hydrophilic colloid such as gelatin can be added to improve the stability of the dispersion.

  Examples of the dispersion apparatus that can be used to prepare the dispersion include a high speed stirring type disperser described in FIG. 1 of JP-A-4-125561, a ball mill, a sand mill, an ultrasonic disperser, and the like. be able to.

  Further, when using these dispersing apparatuses, as described in JP-A-4-125632, a pre-treatment such as dry pulverization is performed in advance, followed by wet dispersion.

  The silver halide emulsion used in the present invention may contain one or a combination of two or more sensitizing dyes.

  The coupler used in the silver halide color photographic material according to the present invention may be any coupler capable of forming a coupling product having a spectral absorption maximum wavelength in a wavelength region longer than 340 nm by a coupling reaction with an oxidized color developing agent. Although a compound can also be used, a typical example is a yellow dye-forming coupler having a spectral absorption maximum wavelength in a wavelength range of 350 to 500 nm, and a magenta dye-forming coupler having a spectral absorption maximum wavelength in a wavelength range of 500 to 600 nm. Typical examples of cyan dye-forming couplers having a spectral absorption maximum wavelength in the wavelength range of 600 to 750 nm are typical.

  As the magenta coupler used in the light-sensitive material according to the present invention, a compound represented by the general formula [M-1] described in the right column of page 7 of JP-A-6-95283 is preferable because of its good spectral absorption characteristics. Specific examples of the preferred compound include compounds M-1 to M-19 described on pages 8 to 11 of the same. As other specific examples, compounds M-1 to M-61 described in European Patent No. 0273712, pages 6 to 21 and compounds 1 to 223 described in JP 0235913, pages 36 to 92 are described above. There are other than the typical examples.

The magenta coupler can also be used in combination with other types of magenta couplers and is usually 1 × 10 ⁻³ mol to 1 mol, preferably 1 × 10 ⁻² mol to 8 × 10 ⁻¹ mol, per mol of silver halide. Can be used in a range.

  The λmax of spectral absorption of the magenta image formed in the photosensitive material according to the present invention is preferably 530 to 560 nm, and λL0.2 is preferably 580 to 635 nm. λL0.2 is a wavelength on the spectral absorbance curve of the magenta image that is longer than the wavelength at which the maximum absorbance is 1.0 and the absorbance is 0.2.

  The magenta image forming layer of the silver halide color light-sensitive material according to the present invention preferably contains a yellow coupler in addition to the magenta coupler. The difference in pKa between these couplers is preferably within 2 and more preferably within 1.5. A preferred yellow coupler to be contained in the magenta image forming layer of the present invention is a coupler represented by the general description [Y-Ia] described in JP-A-6-95283, page 12, right column. Of the couplers represented by the general formula [Y-1] of the same publication, a coupler represented by [M-1] is preferable when combined with a magenta coupler represented by the general formula [M-1]. The coupler has a pKa value not lower than 3 or lower than the pKa value not lower than 3 pKa.

  Specific examples of the yellow coupler include compounds Y-1 and Y-2 described on pages 12 to 13 of JP-A-6-95283 and compounds described on pages 13 to 17 of JP-A-2-139542 ( Y-1) to (Y-58) can be preferably used, but of course not limited thereto.

  As a cyan coupler that can be preferably used in the cyan image forming layer of the light-sensitive material according to the present invention, a pyrrolotriazole coupler is preferably used, which is represented by the general formula (I) or (II) in JP-A-5-313324. The couplers represented by formula (I) of JP-A-6-347960 and the exemplified couplers described in these patents are particularly preferred. Phenol-based and naphthol-based cyan couplers are also preferable. For example, cyan couplers represented by the general formula (ADF) described in JP-A-10-333297 are preferable. Examples of cyan couplers other than those described above include pyrroloazole type cyan couplers described in European Patent Nos. 488,248 and 491,197 A1, and 2,5 described in US Pat. No. 5,888,716. -Diacylaminophenol coupler, pyrazoloazole type cyan coupler having an electron-withdrawing group and a hydrogen-bonding group at the 6-position described in US Pat. Nos. 4,873,183 and 4,916,051 In particular, pyrazoloazole type cyan couplers having a carbamoyl group at the 6-position described in JP-A-8-171185, JP-A-8-31360, and JP-A-8-339060 are also preferable.

  In addition to the diphenylimidazole cyan coupler described in JP-A-2-33144, 3-hydroxypyridine cyan couplers described in European Patent No. 333,185A2 (particularly couplers listed as specific examples ( 42) 4-equivalent couplers having a chlorine-eliminating group to give 2 equivalents, couplers (6) and (9) are particularly preferred) and cyclic active methylene cyanides described in JP-A No. 64-32260. Couplers (among others, coupler examples 3, 8, and 34 listed as specific examples are particularly preferred), pyrrolopyrazole type cyan couplers described in EP 456,226A1, and EP 484,909. A pyrroloimidazole type cyan coupler can also be used.

  Of these cyan couplers, pyrroloazole cyan couplers represented by the general formula (I) described in JP-A No. 11-282138 are particularly preferred. Paragraph Nos. [0012] to [0059] of the patent. The description including the cyan couplers (1) to (47) is applied to the present application as it is, and is preferably incorporated as part of the specification of the present application.

The cyan coupler can usually be used in the silver halide emulsion layer in the range of 1 × 10 ⁻³ to 1 mol, preferably 1 × 10 ⁻² to 8 × 10 ⁻¹ mol, per mol of silver halide.

  As the yellow coupler contained in the yellow image forming layer in the light-sensitive material according to the present invention, known acylacetanilide couplers can be preferably used.

  Specific examples of the yellow coupler include compounds described in pages 5 to 9 of JP-A-3-241345, compounds represented by YI-1 to Y-I-55, or JP-A-3-209466. The compounds described on pages 11 to 14 and the compounds represented by Y-1 to Y-30 can also be preferably used. Furthermore, couplers represented by the general formula [Y-I] described on page 21 of JP-A-6-95283, compounds of general formulas (I) and (II) described in JP-A-2002-352023, and the like can also be mentioned. .

  The λmax of the spectral absorption of the yellow image formed by the photosensitive material according to the present invention is preferably 425 nm or more, and λL0.2 is preferably 515 nm or less.

  The spectral absorption λL0.2 of the yellow color image is a value defined by the contents described in JP-A-6-95283, page 21, right column, lines 1 to 24, and is a long wave in the spectral absorption characteristics of the yellow dye image. Indicates the size of unnecessary absorption on the side.

The yellow coupler can usually be used in the silver halide emulsion layer in the range of 1 × 10 ⁻³ to 1 mol, preferably 1 × 10 ⁻² to 8 × 10 ⁻¹ mol, per mol of silver halide.

  In order to adjust the spectral absorption characteristics of the magenta color image, cyan color image, and yellow color image, it is preferable to add a compound having a color tone adjusting action. As the compound for this purpose, a phosphoric acid ester compound represented by the general formula [HBS-I] described in JP-A-6-95283, page 22 and a phosphine oxide compound represented by [HBS-II] are more preferable. A compound represented by the general formula [HBS-II] described on page 22 of the same number is preferred. Further, higher alcohol compounds represented by (ai) to (ax) described on page 5 of JP-A-4-265975 can be raised.

  In the light-sensitive material according to the present invention, the silver halide emulsion layer is laminated and coated on a support, but the order from the support may be any order. In addition to this, an intermediate layer, a filter layer, a protective layer, and the like can be disposed as necessary.

  Each of the magenta, cyan, and yellow couplers can be used in combination with an anti-fading agent for preventing fading of the formed dye image due to light, heat, humidity, and the like. Preferred compounds include phenyl ether compounds represented by general formulas I and II described on page 3 of JP-A-2-66541, phenolic compounds represented by general formula IIIB described in JP-A-3-174150, Particularly preferred for magenta dyes are amine compounds represented by the general formula A described in No. 90445 and metal complexes represented by the general formulas XII, XIII, XIV and XV described in JP-A No. 62-182741. Further, a compound represented by the general formula I ′ described in JP-A-1-196049 and a compound represented by the general formula II described in JP-A-5-11417 are particularly preferable for yellow and cyan dyes.

  The silver halide emulsion used in the present invention is known for the purpose of preventing fogging that occurs during the preparation process of the silver halide color light-sensitive material, reducing fluctuations in performance during storage, and preventing fogging that occurs during development. Antifoggants and stabilizers can be used. Examples of preferable compounds that can be used for such purposes include compounds represented by the general formula (II) described in JP-A-2-14636, page 7, lower column, and more preferable specific compounds. Are the compounds of (IIa-1) to (IIa-8) and (IIb-1) to (IIb-7) described on page 8 of the same publication, as well as JP 2000-267,235 page 8, right column 32. To the compound described on line 36, a mercaptopyrimidine compound represented by the general formula (I) of JP-A-9-152675, an adsorption promoting group and a substitution with silver halide represented by the general formula (II), Compounds having a substituted hydroxyl group or amino group, specifically, (I-1), (I-2), (I-7), (I-9), (II-1), (II-3) ) Can be mentioned. In addition, compounds having sulfides and polysulfide groups shown in (A) to (D) of JP-A-10-31279 can be mentioned, and specifically, (C-1), (C-9), (C-14), (C-15), (C-16), (D-1), (D-6), α-sulfur, JP-A 2000-122204 (I-4), (I- 6).

Depending on the purpose, these compounds are added in steps such as a silver halide emulsion grain preparation step, a chemical sensitization step, a chemical sensitization step, and a coating solution preparation step. When chemical sensitization is carried out in the presence of these compounds, it is preferably used in an amount of about 1 × 10 ⁻⁵ mol to 5 × 10 ⁻⁴ mol per mol of silver halide. When added at the end of chemical sensitization, the amount is preferably about 1 × 10 ⁻⁶ mol to 1 × 10 ⁻² mol per mol of silver halide, preferably 1 × 10 ⁻⁵ mol to 5 × 10 ⁻³ mol. More preferred. In the coating solution preparation step, when added to the silver halide emulsion layer, the amount of 1 × 10 ^-6 mol to 1 × 10 ^-1 mol per mol of silver halide is preferred, 1 × 10 ^-5 mol to 1 × 10 ⁻² mol is more preferred. When added to a layer other than the silver halide emulsion layer, the amount in the coating film is preferably about 1 × 10 ⁻⁹ mol to 1 × 10 ⁻³ mol per 1 m ² .

  In the silver halide color light-sensitive material according to the present invention, a compound that reacts with an oxidized developing agent is added to the layer between the light-sensitive layer to prevent color turbidity and is added to the silver halide emulsion layer. It is preferable to improve fog and the like. The compound for this purpose is preferably a hydroquinone derivative, more preferably a dialkyl hydroquinone such as 2,5-di-t-octyl hydroquinone. Particularly preferred compounds are compounds represented by the general formula II described in JP-A-4-133056, and examples thereof include compounds II-1 to II-14 described on pages 13 to 14 and compound 1 described on page 17.

  In the light-sensitive material according to the present invention, it is preferable to add an ultraviolet absorber to prevent static fogging or to improve the light resistance of a dye image. Preferred ultraviolet absorbers include benzotriazoles. Particularly preferred compounds are compounds represented by general formula III-3 described in JP-A-1-250944, and compounds represented by general formula III described in JP-A 64-66646. Compounds represented by general formula I described in JP-A No. 63-187240, UV-1L to UV-27L described in JP-A No. 63-187240, general formula I described in JP-A No. 4-1633, general formula (I) described in JP-A No. 5-165144, The compound shown by (II) is mentioned.

  When an oil-in-water emulsion dispersion method is used to add the coupler, stain inhibitor and other organic compounds used in the silver halide color photographic material according to the present invention, water having a boiling point of 150 ° C. or higher is usually used. A low-boiling and / or water-soluble organic solvent is dissolved in an insoluble high-boiling organic solvent as necessary, and emulsified and dispersed in a hydrophilic binder such as an aqueous gelatin solution using a surfactant. As the dispersing means, a stirrer, a homogenizer, a colloid mill, a flow jet mixer, an ultrasonic disperser, or the like can be used. A step of removing the low-boiling organic solvent after the dispersion or simultaneously with the dispersion may be added. As high-boiling organic solvents that can be used to dissolve and disperse stain inhibitors, phosphate esters such as tricresyl phosphate and trioctyl phosphate, and phosphine oxides such as trioctyl phosphine oxide are preferably used. It is done. The dielectric constant of the high boiling point organic solvent is preferably 3.5 to 7.0. Two or more high-boiling organic solvents can be used in combination.

  In the photosensitive material used in the present invention, dyes having absorption in various wavelength ranges can be used for the purpose of preventing irradiation and preventing halation. For this purpose, any known compound can be used. In particular, as dyes having absorption in the visible region, the dyes AI-1 to 11 described in JP-A-3-251840, page 308 and JP-A-6 A dye described in No. 3770 is preferably used.

  The silver halide color light-sensitive material according to the present invention has a hydrophilicity colored with at least one non-diffusible compound on the side closer to the support than the silver halide emulsion layer closest to the support in the silver halide emulsion layer. It preferably has a colloid layer. As the coloring substance, a dye or other organic or inorganic coloring substance can be used.

  The light-sensitive material of the present invention preferably has at least one layer containing 35% by weight or more of a white pigment between the support and the silver halide emulsion layer closest to the support. As the white pigment, for example, rutile type titanium dioxide, anatase type titanium dioxide, barium sulfate, barium stearate, silica, alumina, zirconium oxide, kaolin and the like can be used. Type titanium dioxide is preferred. The white pigment is dispersed in an aqueous binder of hydrophilic colloid such as gelatin so that the treatment liquid can penetrate. The content of the white pigment is preferably 40% by mass or more, and more preferably 60% by mass or more. However, when the content is more than this, troubles occur in terms of brittleness and applicability. The white pigment layer may contain the coloring substance.

The coating with the amount of the white pigment is preferably in the range of ^{0.1g / m 2 ~50g / m 2} , more preferably in the range of ^{0.2g / m 2 ~5g / m 2} .

  Between the support and the silver halide emulsion layer closest to the support, in addition to the white pigment-containing layer, an undercoat layer as required, or a non-photosensitive hydrophilic colloid layer such as an intermediate layer at an arbitrary position Can be provided.

  Addition of a fluorescent brightening agent to the silver halide color photographic material according to the present invention is preferred because the white background can be further improved. The fluorescent whitening agent is not particularly limited as long as it is a compound that can absorb ultraviolet rays and emit visible light fluorescence, but is a diaminostilbene compound having at least one sulfonic acid group in the molecule, These compounds are preferable because they have an effect of promoting the elution of the sensitizing dye to the outside of the photosensitive material. Another preferred form is a solid particulate compound having a fluorescent whitening effect.

  As a preferable compound as a surfactant used for dispersion of photographic additives used in the light-sensitive material according to the present invention and adjustment of surface tension during coating, a hydrophobic group having 8 to 30 carbon atoms and sulfone in one molecule. The thing containing an acid group or its salt is mentioned. Specific examples include A-1 to A-11 described in JP-A No. 64-26854. A surfactant in which a fluorine atom is substituted for an alkyl group is also preferably used. These dispersions are usually added to a coating solution containing a silver halide emulsion, but the time until the addition to the coating solution after dispersion and the time after the addition to the coating solution are preferably shorter, and each time is 10 hours. Is preferably within 3 hours, and more preferably within 20 minutes.

  The light-sensitive material according to the present invention preferably contains an oil-soluble dye or pigment, since the white background is improved. Typical examples of oil-soluble dyes include compounds 1-27 described in JP-A-2-842, pages 8-9.

  In the silver halide color light-sensitive material according to the present invention, it is advantageous to use gelatin as a binder, but other gelatins, gelatin derivatives, graft polymers of gelatin and other polymers, and proteins other than gelatin as necessary. Hydrophilic colloids such as sugar derivatives, cellulose derivatives, synthetic hydrophilic polymer materials such as mono- or copolymers can also be used.

  As the binder hardener, it is preferable to use a vinylsulfone type hardener or a chlorotriazine type hardener alone or in combination. It is preferable to use compounds described in JP-A Nos. 61-249054 and 61-245153. It is preferable to add a preservative and an antifungal agent as described in JP-A-3-157646 in the colloid layer in order to prevent the growth of mold and bacteria that adversely affect photographic performance and image storage stability. In order to improve the physical properties of the surface of the photosensitive material or the processed sample, it is preferable to add a slipping agent or a matting agent described in JP-A-6-118543 or JP-A-2-73250 to the protective layer.

  As the support used for the photosensitive material according to the present invention, any material may be used, such as paper coated with polyethylene or polyethylene terephthalate, paper support made of natural pulp or synthetic pulp, vinyl chloride sheet, white pigment. Polypropylene, polyethylene terephthalate support, baryta paper and the like which may be contained can be used. Especially, the support body which has a water-resistant resin coating layer on both surfaces of a base paper is preferable. As the water resistant resin, polyethylene, polyethylene terephthalate or a copolymer thereof is preferable.

As the support having a water-resistant resin coating layer on the surface of paper, a smooth surface having a mass of 50 to 300 g / m ² is usually used, but for the purpose of obtaining a proof image, a feeling of handling to approximate the printing paper, 130 g / m ² or less of the base paper is preferably used, it is preferably used further 70~120g / m ² base paper.

  The support used in the present invention can be preferably used even if it has random irregularities or is smooth.

  As the white pigment used for the support, inorganic and / or organic white pigments can be used, and inorganic white pigments are preferably used. For example, alkaline earth metal sulfate such as barium sulfate, alkaline earth metal carbonate such as calcium carbonate, silica such as fine silicate, synthetic silicate, calcium silicate, alumina, alumina hydrate, oxidation Examples include titanium, zinc oxide, talc, and clay. The white pigment is preferably barium sulfate or titanium oxide.

  The amount of the white pigment contained in the water-resistant resin layer on the surface of the support is preferably 13% by mass or more, and more preferably 15% by mass for improving sharpness.

  The degree of dispersion of the white pigment in the water-resistant resin layer of the paper support according to the present invention can be measured by the method described in JP-A-2-28640. When measured by this method, the degree of dispersion of the white pigment is preferably 0.20 or less, and more preferably 0.15 or less, as the coefficient of variation described in the above publication.

  The resin layer of the paper support having water-resistant resin layers on both sides used in the present invention may be a single layer or a plurality of layers. When a plurality of layers are used and a white pigment is contained at a high concentration in the contact with the emulsion layer, sharpness is greatly improved, which is preferable for forming a proof image.

  Further, it is more preferable that the value of the center plane average roughness (SRa) of the support is 0.15 μm or less, and further 0.12 μm or less, because the effect of good gloss is obtained.

  The photographic light-sensitive material used in the present invention is subjected to corona discharge, ultraviolet irradiation, flame treatment, etc. on the support surface as necessary, and then directly or undercoat layer (adhesion of the support surface, antistatic properties, dimensions). One or more subbing layers for improving the degree of stability, rub resistance, hardness, antihalation, friction properties and / or other properties.

  When coating a photographic light-sensitive material using a silver halide emulsion, a thickener may be used to improve the coating property. As the coating method, extrusion coating and curtain coating capable of simultaneously coating two or more layers are particularly useful.

  As the width of the photosensitive material, a material having an arbitrary width can be used according to the use, but a width of 400 mm or more is preferably used for the proof use. A photosensitive material having a width of 800 mm or more is also preferably used.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto. In addition, although the display of "part" or "%" is used in an Example, unless otherwise indicated, "part by mass" or "mass%" is represented.

Example 1
<< Preparation of silver halide color photosensitive material >>
A polyethylene laminated paper reflective support (Taber stiffness) with a mass per square meter of 115 g of laminated high-density polyethylene on one side and molten polyethylene containing 15% by mass of anatase-type titanium oxide dispersed on the other side. = 3.5, PY value = 2.7 μm), each layer having the composition shown in Table 1 below was coated on the side of the polyethylene layer containing titanium oxide, and further on the back side was 7.20 g / gelatin. A layer containing m ² and a silica matting agent 0.65 g / m ² was applied to prepare Sample 101 which is a multilayer silver halide color photosensitive material. At this time, on the back side was added so that as a hardening agent (H-2) and 0.05 g / m ^2.

The coupler and the stain inhibitor were dissolved in a high boiling point solvent and ultrasonically dispersed and added as a dispersion. At this time, (SU-1) was used as a surfactant. Further, the ultraviolet absorber was also ultrasonically dispersed and added as a dispersion. Moreover, (H-1) and (H-2) were added as a hardening agent. Moreover, (F-1) was added to each layer so that the whole quantity might be set to 0.04 g / m < ² >.

  As coating aids, surfactants (SU-2) and (SU-3) were added to adjust the surface tension.

SU-1: Sodium tri-i-propylnaphthalene sulfonate SU-2: Sulfosuccinic acid di (2-ethylhexyl) sodium salt SU-3: Sulfosuccinic acid di (2,2,3,3,4,4,4) 5,5-octafluoropentyl) sodium salt H-1: tetrakis (vinylsulfonylmethyl) methane H-2: 2,4-dichloro-6-hydroxy-s-triazine sodium HQ-1: 2,5-di -T-octylhydroquinone HQ-2: 2,5-di ((1,1-dimethyl-4-hexyloxycarbonyl) butyl) hydroquinone HQ-3: 2,5-di-sec-dodecylhydroquinone and 2,5- A mixture of di-sec tetradecyl hydroquinone and 2-sec-dodecyl-5-sec-tetradecyl hydroquinone in a mass ratio of 1: 1: 2. Q-4: 2,5-di -t- butyl hydroquinone PVP: Polyvinylpyrrolidone

  Each photosensitive silver halide emulsion used for the preparation of Sample 101 was prepared according to the following method.

(Preparation of blue-sensitive silver halide emulsion)
In 1 liter of 2% gelatin aqueous solution kept at 40 ° C., the following (A solution) and (B solution) were simultaneously added while controlling pAg = 7.3 and pH = 3.0, and the following (C solution) And (Liquid D) were simultaneously added while controlling pAg = 8.0 and pH = 5.5. At this time, pAg was controlled according to the method described in JP-A-59-45437, and pH was controlled using sulfuric acid or a sodium hydroxide aqueous solution.

<Liquid A>
Sodium chloride 3.42g
Potassium bromide 0.03g
Water added to finish 200ml <Liquid B>
Silver nitrate 10g
Water added to finish 200ml <C solution>
Sodium chloride 102.7g
Potassium hexachloroiridium (IV) 4 × 10 ⁻⁸ mol Potassium hexacyanoferrate (II) 2 × 10 ⁻⁵ mol Potassium bromide 1.0 g
Water added to finish 600ml <Liquid D>
300 g of silver nitrate
Finished by adding water to 600 ml. After completion of addition, desalting was performed using a 5% aqueous solution of demole N and 20% aqueous solution of magnesium sulfate manufactured by Kao Atlas, and then mixed with an aqueous gelatin solution to obtain an average particle size. A monodispersed cubic emulsion EMP-101 having 0.71 μm, a coefficient of variation of grain size distribution of 0.07, and a silver chloride content of 99.5 mol% was obtained.

  The emulsion EMP-101 was optimally chemically sensitized at 60 ° C. using the following compound to obtain a blue-sensitive silver halide emulsion Em-B101.

Sodium thiosulfate 0.8mg / mol AgX
Chloroauric acid 0.5mg / mol AgX
Stabilizer: STAB-1 3 × 10 ⁻⁴ mol / mol AgX
Stabilizer: STAB-2 3 × 10 ⁻⁴ mol / mol AgX
Stabilizer: STAB-3 3 × 10 ⁻⁴ mol / mol AgX
Sensitizing dye: BS-1 4 × 10 ⁻⁴ mol / mol AgX
Sensitizing dye: BS-2 1 × 10 ⁻⁴ mol / mol AgX
Potassium bromide 0.2g / mol AgX
Next, in the preparation of the emulsion EMP-101, the average grain size was changed in the same manner except that the addition times of (A liquid) and (B liquid) and (C liquid) and (D liquid) were changed. A monodispersed cubic emulsion EMP-102 having a diameter of 0.64 μm, a coefficient of variation of the particle size distribution of 0.07, and a silver chloride content of 99.5 mol% was obtained.

  A blue-sensitive silver halide emulsion Em-B102 was prepared in the same manner as in the preparation of the blue-sensitive silver halide emulsion Em-B101, except that the emulsion EMP-102 was used instead of the emulsion EMP-101. A blue-sensitive silver halide emulsion using a 1: 1 mixture of -B101 and Em-B102 in the sixth layer was prepared.

(Preparation of green sensitive silver halide emulsion)
In the preparation of the emulsion EMP-101, the average particle size of 0 was similarly obtained except that the addition times of (A liquid) and (B liquid) and (C liquid) and (D liquid) were changed. A monodisperse cubic emulsion EMP-103 having a thickness of .40 μm, a coefficient of variation of 0.08, and a silver chloride content of 99.5% was obtained.

  The above emulsion EMP-103 was optimally chemically sensitized at 55 ° C. using the following compound to obtain green photosensitive silver halide emulsion Em-G101.

Sodium thiosulfate 1.5mg / mol AgX
Chloroauric acid 1.0mg / mol AgX
Stabilizer: STAB-1 3 × 10 ⁻⁴ mol / mol AgX
Stabilizer: STAB-2 3 × 10 ⁻⁴ mol / mol AgX
Stabilizer: STAB-3 3 × 10 ⁻⁴ mol / mol AgX
Sensitizing dye: GS-1 1 × 10 ⁻⁴ mol / mol AgX
Sensitizing dye: GS-2 1 × 10 ⁻⁴ mol / mol AgX
Sensitizing dye: GS-3 2 × 10 ⁻⁴ mol / mol AgX
Sodium chloride 0.5g / mol AgX
Subsequently, in the preparation of the emulsion EMP-103, the average particle size was changed in the same manner except that the addition time of (Liquid A) and (Liquid B) and the addition time of (Liquid C) and (Liquid D) were changed. A monodispersed cubic emulsion EMP-104 having a 0.50 μm, a coefficient of variation of 0.08 and a silver chloride content of 99.5% was obtained.

  A green-sensitive silver halide emulsion Em-G102 was prepared in the same manner as in the preparation of the green-sensitive silver halide emulsion Em-G101, except that EMP-104 was used instead of EMP-103. Em-G101 and Em -A green-sensitive silver halide emulsion using a 1: 1 mixture of G102 in the fourth layer.

(Preparation of red-sensitive silver halide emulsion)
The prepared emulsion EMP-103 was optimally chemically sensitized at 60 ° C. using the following compound to obtain a red-sensitive silver halide emulsion Em-R101.

Sodium thiosulfate 1.8mg / mol AgX
Chloroauric acid 2.0mg / mol AgX
Stabilizer: STAB-1 2 × 10 ⁻⁴ mol / mol AgX
Stabilizer: STAB-2 2 × 10 ⁻⁴ mol / mol AgX
Stabilizer: STAB-3 2 × 10 ⁻⁴ mol / mol AgX
Stabilizer: STAB-4 1 × 10 ⁻⁴ mol / mol AgX
Sensitizing dye: RS-1 1 × 10 ⁻⁴ mol / mol AgX
Sensitizing dye: RS-2 1 × 10 ⁻⁴ mol / mol AgX
Supersensitizer: SS-1 2 × 10 ⁻⁴ mol / mol AgX
Next, the prepared emulsion EMP-103 was optimally chemically sensitized at 60 ° C. using the following compound to obtain a red-sensitive silver halide emulsion Em-R102.

Sodium thiosulfate 1.8mg / mol AgX
Chloroauric acid 2.0mg / mol AgX
Stabilizer: STAB-1 2 × 10 ⁻⁴ mol / mol AgX
Stabilizer: STAB-2 2 × 10 ⁻⁴ mol / mol AgX
Stabilizer: STAB-3 2 × 10 ⁻⁴ mol / mol AgX
Stabilizer: STAB-4 1 × 10 ⁻⁴ mol / mol AgX
Sensitizing dye: RS-1 2 × 10 ⁻⁴ mol / mol AgX
Sensitizing dye: RS-2 2 × 10 ⁻⁴ mol / mol AgX
Supersensitizer: SS-1 2 × 10 ⁻⁴ mol / mol AgX
A 1: 1 mixture of the red-sensitive silver halide emulsion Em-R101 and the red-sensitive silver halide emulsion Em-R102 prepared above was used as the red-sensitive silver halide emulsion for the third layer.

  Details of the additives used in the preparation of each of the above photosensitive silver halide emulsions are as follows.

STAB-1: 1-phenyl-5-mercaptotetrazole STAB-2: 1- (4-Ethoxyphenyl) -5-mercaptotetrazole STAB-3: 1- (3-acetamidophenyl) -5-mercaptotetrazole STAB-4: p-Toluenethiosulfonic acid

"exposure"
The prepared sample 101 is cut to a width of 670 mm and a length of 52 m, and is wound around a cylindrical core having an outer diameter of 80 mm with the silver halide photosensitive layer coating surface on the outer side. A 6 cm wide light-shielding sheet was attached, and it was further wound three times, and fixed so as not to loosen.

  The roll-shaped sample 101 produced in this way was loaded into a photosensitive material cartridge for Digital Konsensus Pro manufactured by Konica Minolta MG Co., Ltd., and set in the same exposure apparatus. When loading the cartridge, the light-shielding sheet was released from the fixing state, and the light-shielding sheet was loaded so that the tip of the light-shielding sheet protrudes from the groove of the cartridge, taking care not to loosen and expose the photosensitive material. After loading, the light shielding sheet was pulled out until the photosensitive material portion was exposed, and unnecessary portions were cut, and then loaded into the exposure apparatus.

  As the image data, the above-described exposure apparatus performed wedge exposure with a width of 10 mm under the exposure conditions in which the minimum light amount to the maximum light amount were divided into 18 parts, and the following development processing was performed.

<Development processing>
[Development processing 1]
The prepared sample 101 was conveyed to an automatic developing machine and subjected to the following development processing. In the stabilization process, the temperatures in the first and third tanks were not controlled, and only the second tank was set at 37 ° C. The processing was continuously performed for 60 days until the replenishment amount of the color developer became one time the color development tank capacity (18 L) (hereinafter referred to as one round). The processing conditions per day were set at a set temperature and left for 12 hours, and then processed for 4 hours while replenishing each processing tank with pure water as a replenishing solution every 20 ml per hour. .

  Further, as the silver halide color photographic material processed in the continuous processing, the sample 101 subjected to the wedge exposure under the exposure condition in which the minimum light amount to the maximum light amount was divided into 18 using the above exposure apparatus was used.

(Processing conditions)
Processing process Processing temperature Processing time Tank capacity Replenishment volume (ml / m ² )
Color development 40.0 ± 0.3 ° C 100 seconds 18L 150ml
Bleach fixing 40.0 ± 0.5 ℃ 50 seconds 8L 75ml
Stabilization-1 40.0 ± 0.5 ° C 30 seconds 5L-
Stabilization-2 40.0 ± 0.5 ° C 30 seconds 5L-
Stabilization-3 40.0 ± 0.5 ° C 30 seconds 5L 150ml
Drying 60-80 ° C 30 seconds * 1) Stabilization 2 → Cascade flow to stabilization 1 * 2) Stabilization 3 → Cascade flow to stabilization 2 To the time from when the tip enters the next tank.

(Each treatment composition)
The treatment liquids used in the above treatment steps are as follows.

<Color developer tank solution and replenisher>
Tank liquid Replenisher Triethylenediamine 3.0 g 4.0 g
Diethylene glycol 6.0g 8.0g
Potassium bromide 0.15g 0.2g
Potassium chloride 3.5g 0.2g
Potassium sulfite 0.3g 0.4g
4-Amino-3-methyl-N-ethyl-N-β-methanesulfonamidoethylaniline 1.5 sulfate monohydrate 3.0 g 4.0 g
N, N-disulfoethylhydroxylamine 15.0 g 20.0 g
Diethylenetriaminepentaacetic acid sodium salt 1.5 g 2.0 g
Potassium carbonate 30g 40g
Water was added to a total volume of 1 liter, and the tank solution was adjusted to pH = 10.2 with sulfuric acid or potassium hydroxide, and the replenisher was adjusted to pH = 10.5.

<Bleach fixer tank solution and replenisher>
Tank liquid = replenisher diethylenetriaminepentaacetic acid ferric ammonium dihydrate 65g
Diethylenetriaminepentaacetic acid 3.0g
Ammonium thiosulfate (75% aqueous solution) 120 g 100 ml
2-amino-5-mercapto-1,3,4-thiadiazole 2.0 g
Ammonium sulfite (40% aqueous solution) 27.5 ml
Water was added to bring the total volume to 1 liter, and the pH was adjusted to 5.0 with potassium carbonate or glacial acetic acid.

<Stabilizing liquid tank liquid and replenisher liquid>
Tank liquid = replenisher diethylene glycol 1.0g
1-hydroxyethylidene-1,1-diphosphonic acid 1.8 g
Zinc sulfate 0.5g
Magnesium sulfate heptahydrate 0.2g
PVP (Polyvinylpyrrolidone) 1.0g
Ammonia water (25% ammonium hydroxide aqueous solution) 2.5 g
Nitrilotriacetic acid trisodium salt 1.5g
Water was added to make the total volume 1 liter, and the pH was adjusted to 7.5 with sulfuric acid or aqueous ammonia.

<Replenisher>
Using pure water, each of the color developing tank, the bleach-fixing tank, and the three-layer stabilizing tank was replenished according to the method shown in FIG.

[Development processing 2]
In the above-mentioned development processing 1, in place of pure water, an aqueous solution prepared by dissolving 0.5 g of chlorinated isocyanurate sodium per liter of pure water was used in the same manner as the replenisher (this is referred to as antibacterial means 1). This was designated as development processing 2.

[Development processing 3]
In the development processing 1, an aqueous solution in which 0.5 g of 2-methyl-5-chloro-4-isothiazolin-3-one was dissolved per 1 L of pure water was used as a replenishing solution instead of pure water ( Except for the antibacterial means 2), this was the same as development processing 3.

[Development processing 4-8]
In the above development treatment 1, a silver elution cartridge comprising a porous film carrying a sparingly soluble silver compound having the structure described in FIG. 2 of JP-A No. 2001-25772 instead of pure water as a replenisher solution ( This was designated as development treatments 4 to 8 in the same manner except that the antibacterial means 3) was used and a rehydration solution containing silver ion concentrations of 5 ppb, 15 ppb, 100 ppb, 800 ppb and 1100 ppb, respectively.

[Development processing 9-13]
In the above development processing 1, instead of pure water as a replenisher, a silver elution cartridge composed of silver-impregnated activated carbon having the structure described in FIG. 1 of JP-A-10-314754 (this is referred to as antibacterial means 4) This was designated as development processes 9 to 13 in the same manner except that a water replenisher containing 5 ppb, 15 ppb, 100 ppb, 800 ppb and 1100 ppb was used as the silver ion concentration.

[Development processing 14-18]
In the above development treatment 1, instead of pure water as a replenisher, a silver elution cartridge composed of silver-plated fibers having the structure described in FIG. 2 of JP-A-8-71338 (this is referred to as antibacterial means 5) In the same manner, a rehydration solution containing 5 ppb, 15 ppb, 100 ppb, 800 ppb, and 1100 ppb as silver ion concentrations was used, and this was designated as development processing 14-18.

[Development processing 19-23]
In the development process 1 described above, instead of pure water, an electrolytic silver ion eluting device (referred to as antibacterial means 6) having the structure shown in FIG. 1 of JP-A-8-257567 is used as a replenisher solution. These were designated as development treatments 14 to 18 in the same manner except that the replenishing solution containing 5 ppb, 15 ppb, 100 ppb, 800 ppb, and 1100 ppb as silver ion concentrations was used.

<Evaluation>
About the said development processes 1-23, the process stain | pollution | contamination tolerance and the process stability were evaluated in accordance with the following method.

[Evaluation of scale resistance]
After the continuous processing according to the above method, the inner wall surface of the color developing tank and the surface of the transport roller were checked visually and with a finger to confirm the presence or absence of scale generation, and the scale resistance was evaluated according to the following criteria. .

◎: No generation of scale is observed, and it is in a very good state. ○: Almost no generation of scale is observed on the inner wall of the color developer interface and the transport roller. △: The inner wall of the color developer interface and Slight generation of water is confirmed on a part of the surface of the transport roller, but the quality is acceptable for practical use. ×: Clearly on the inner wall of the color developer interface and part of the surface of the transport roller The occurrence of scale is confirmed and is a quality that is a problem in practice. XX: Scale is generated over the entire inner wall of the color developer interface and the surface of the transport roller, and the quality is not practical. (Evaluation of processing dirt resistance)
When performing continuous treatment over 60 days, on the 20th day, 40th day, and 60th day, 5 pieces of each of the A1 size samples 101 were treated, and the state of dirt adhesion on the sample surface was visually observed. In accordance with the criteria, the processing stain resistance was evaluated.

A: No contamination on the sample surface was confirmed until the 60th day of continuous use. ○: No soiling was observed until the 40th day of continuous use, but slight contamination was confirmed on the 60th day. Slight dirt adhesion was confirmed on the 40th consecutive day, and the dirt gradually increased until the 60th day, but the quality is acceptable for practical use. X: The dirt adhesion was confirmed on the 20th consecutive day, the 40th day, Dirty is considerably increased up to the 60th day, and is a quality that is a problem in practical use. XX: A large amount of dirt adhesion was confirmed on the 20th consecutive day, and the quality was unbearable. [Evaluation of processing stability]
Immediately after the start of the continuous process and at the end of the continuous process, after processing each sample subjected to the wedge exposure under the exposure condition obtained by dividing the light quantity from the minimum light quantity to the maximum light quantity using the exposure apparatus, X The reflection density was measured with a -rite densitometer, and a characteristic curve consisting of vertical axis: color density and horizontal axis: exposure amount was prepared.

  In the created characteristic curve, the exposure dose point at which the yellow density, magenta density and cyan density processed immediately after the start of continuous processing is 1.0 is Log E, and the yellow density and magenta at each Log E of the sample processed at the end of continuous processing Density and cyan density were measured and used as a measure of processing stability. The closer each concentration is to 1.00, the better the processing stability is.

  The results obtained as described above are shown in Table 2.

  As is clear from the results shown in Table 2, the development processing of the present invention in which the continuous processing was performed using a replenishing water supply device provided with each silver ion elution means in the water tank was a color developing tank. It can be seen that the generation of water scale is suppressed, the processing stain resistance is excellent, and stable processing characteristics can be obtained without affecting the development characteristics in the continuous processing process even when water is replenished.

Example 2
In the development treatments 1 to 23 of Example 1, water replenishment described in Example 1 was performed only in the color developing tank, and continuous processing was performed by replenishing pure water in the other processing tanks. Similar to the result of the above, compared to the comparative example, the generation of scale in the color developing tank is suppressed, the processing stain resistance is excellent, and even if rehydration is performed, stable processing characteristics are obtained without affecting the development characteristics in the continuous processing process. It was confirmed that it was obtained.

It is a schematic block diagram which shows an example of the image development processing part of the automatic processor used by this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Liquid tank 1A Color development tank 1B Bleach fixing tank 1C 1st stabilization tank 1D 2nd stabilization tank 1E 3rd stabilization tank 2 Auxiliary tank 2A Color development auxiliary tank 2B Bleach fixing auxiliary tank 2C 1st stability auxiliary tank 2D 2nd stability assistance Tank 2E Third stability auxiliary tank 3A Replenishment color developer supply unit 3B Replenishment bleach-fixing agent supply unit 3E Replenishment stabilizer supply unit 4 Photosensitive material transport unit 6 Drying unit 7 Replenisher solution supply pipe 8 Automatic processor H Silver ion elution means Equipped with a replenisher supplying device P Silver halide color photosensitive material

Claims (13)

A water replenisher supply device for an automatic developing machine for silver halide color photographic materials, characterized in that silver ion elution means is provided in the water replenishment tank. 2. The replenishing solution supply of an automatic processor for silver halide color photographic materials according to claim 1, wherein said silver ion elution means is a silver elution cartridge constituted by a porous film carrying a hardly soluble silver compound. apparatus. 2. A replenisher supplying apparatus for an automatic processor for silver halide color photographic materials according to claim 1, wherein said silver ion elution means is a silver elution cartridge composed of silver impregnated activated carbon. 2. A replenisher supplying apparatus for an automatic processor for silver halide color photographic materials according to claim 1, wherein said silver ion elution means is a silver elution cartridge composed of silver plated fibers. 2. A replenisher supplying apparatus for an automatic developing machine for silver halide color photographic materials according to claim 1, wherein said silver ion eluting means is an electrolytic silver ion eluting apparatus. A silver halide color photographic material is processed by replenishing at least one processing tank of an automatic processor with a replenishing liquid containing silver ions eluted from a silver ion elution means in a replenishing tank. Processing method of silver color photosensitive material. 7. The method for processing a silver halide color photographic material according to claim 6, wherein the processing tank for replenishing the replenishing solution containing silver ions is a color developing tank. 7. The method for processing a silver halide color photographic material according to claim 6, wherein the processing tank for replenishing the replenishing solution containing silver ions is a color developing tank, a bleach-fixing tank, a washing tank or a stabilizing tank. 9. The silver halide color photosensitive material according to claim 6, wherein the silver ion elution means is a silver elution cartridge composed of a porous film carrying a hardly soluble silver compound. Processing method. 9. The method for processing a silver halide color photographic material according to claim 6, wherein the silver ion elution means is a silver elution cartridge constituted by silver-impregnated activated carbon. 9. The method for processing a silver halide color light-sensitive material according to claim 6, wherein the silver ion elution means is a silver elution cartridge composed of silver-plated fibers. 9. The method for processing a silver halide color photographic material according to claim 6, wherein the silver ion eluting means is an electrolytic silver ion eluting device. The silver halide color photosensitive material processing method according to any one of claims 6 to 12, wherein a silver ion concentration of the replenishing liquid is 10 ppb or more and 1000 ppb or less.

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