JP2006259489A - Processing method for silver halide color photographic sensitive material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a processing method for a silver halide color photosensitive material in which always stable white ground characteristics can be obtained and white stability is superior even when the amount of a replenisher to replenish is greatly reduced. <P>SOLUTION: The processing method for the silver halide photosensitive material in which the silver halide photosensitive material having been exposed is processed through at least a coloring development stage, a bleaching fixation stage, and a washing stage or stabilization stage is characterized in that a washing tank or stabilizing tank constituting the washing stage or stabilization stage is a multistage counter-flow type comprising three or more layers and at least one of the washing tank and stabilizing tank has an ozone generating device to generate ozonized air bubbles in the washing tank or stabilizing tank for processing. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a method for processing a silver halide color light-sensitive material, and more particularly to a method for processing a silver halide color light-sensitive material having improved white background characteristics of an image output for proofing.

  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.

  In recent years, digitization has progressed in the field of printing, and the demand for obtaining images directly from computer data has increased. For the reasons described above, silver halide light-sensitive materials are advantageously used in this field for proofing purposes. I'm starting. For example, a technique relating to a silver halide photographic material exposed using an exposure apparatus equipped with a specific laser light source unit for the purpose of producing a color proof, and a cartridge for storing the silver halide photographic material is disclosed. (For example, refer to Patent Document 1). Further, a technique relating to an image forming method in which a specific silver halide photographic light-sensitive material is exposed with a specific exposure light source is disclosed (for example, see Patent Document 2). Furthermore, a technique is disclosed in which a silver halide photographic photosensitive sheet is fixed to the outer peripheral surface of the drum, the drum is rotated at a high speed, and exposure is performed by an optical head that irradiates a plurality of beams (see, for example, Patent Document 3). ). In addition, high-definition color proofs are created by increasing the number of halftone dots per unit area when a silver halide photographic photosensitive material wound around the outer surface of a drum is scanned and exposed with a laser. (For example, refer to Patent Document 4). Further, a technique relating to a method for producing a direct digital color proof using a silver halide color light-sensitive material, characterized by using a negative emulsion, is disclosed (for example, see Patent Document 5).

  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.

  Various methods have been proposed in the past as means for improving the white background itself or for suppressing fluctuations of the white background with respect to the white background obtained with the silver halide color light-sensitive material.

  The color proof silver halide color light-sensitive material is generally developed by color washing and bleach-fixing, followed by water washing or stabilization. There is a difference in the quality and stability.

In addition, by performing continuous processing, washing water or stabilizing solution is contaminated by carryover of bleach-fixing solution from the pre-bath, silver halide color light-sensitive material effluent, or evaporation or air oxidation of the processing solution. However, this causes a problem that the silver halide color light-sensitive material to be processed is contaminated. In addition, when performing the continuous treatment while replenishing the replenisher according to the amount of treatment, it is also important to suppress the scales generated in the washing water or the stabilizing liquid. As one of the methods for solving these problems, a treatment method using a multi-stage counter-current system is generally used, and at the same time, the use of an anti-scale agent or the like has been proposed (for example, see Patent Document 6), but it is stable. The replenishment amount of the chemical liquid or the like is naturally limited, and excessive replenishment amount results in an increase in cost and frequency of replenishment operation of the replenisher. Further, when these anti-scale agents are used, they often have an effect on the image formed by the processing, and there is a problem that the fastness of the formed color image is deteriorated.
Japanese Patent Laid-Open No. 11-242299 JP 2000-98544 A JP 2000-180983 A Japanese Patent Application Laid-Open No. 10-142752 Japanese Patent Laid-Open No. 2004-4687 JP 2000-267241 A

  The present invention has been made in view of the above problems, and its object is to always obtain stable white background characteristics, and even if the replenishment amount of the replenisher is greatly reduced, the halogen has excellent white background stability. An object of the present invention is to provide a method for processing a silver halide color light-sensitive material.

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

(Claim 1)
In the processing method of a silver halide color photographic material in which the exposed silver halide color photographic material is processed through at least a color development step, a bleach-fixing step, a water washing step or a stabilization step, the water washing step or the stabilization step is performed. The water washing tank or stabilization tank to be constructed is a multi-stage countercurrent system having three or more layers, at least one of the water washing tank or the stabilization tank has an ozone generator, and the ozonized bubbles are removed from the water washing tank or the stability tank. A method for processing a silver halide color light-sensitive material, which is generated in a crystallization tank and processed.

(Claim 2)
2. The method for processing a silver halide color light-sensitive material according to claim 1, wherein the ozonized bubbles are generated and processed in a final tank of a washing tank or a stabilization tank composed of three or more layers.

(Claim 3)
3. The method for processing a silver halide color photographic material according to claim 1, wherein the water washing tank or the stabilization tank uses electrolyzed water.

  According to the present invention, there is provided a method for processing a silver halide color light-sensitive material that can always obtain stable white background characteristics and has excellent white background stability even when the replenishment amount of the replenisher is greatly reduced. Can do.

  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 present inventor has processed exposed silver halide color light-sensitive materials through at least a color developing step, a bleach-fixing step, a washing step or a stabilizing step. In the color light-sensitive material processing method, the water washing tank or the stabilization tank constituting the water washing process or the stabilization process is a multi-stage countercurrent system having three or more layers, and at least one of the water washing tank or the stabilization tank is ozone. A silver halide color light-sensitive material processing method characterized by having a generator and generating ozonated bubbles in the water washing tank or the stabilizing tank for processing. It is possible to realize a method for processing a silver halide color light-sensitive material excellent in white background stability even if the replenishment amount of the replenisher is remarkably reduced.

  Details of the present invention will be described below.

  First, the details of the processing steps applied to the method for processing a silver halide color photographic material of the present invention (hereinafter also simply referred to as processing method) will be described.

  In the treatment method of the present invention, the water washing tank or the stabilization tank constituting the water washing process or the stabilization process is a multistage countercurrent system having three or more layers, and at least one of the water washing tank or the stabilization tank has an ozone generator. It is characterized by generating and processing ozonated bubbles in a washing tank or stabilization tank, and in particular, ozonized bubbles are generated in the final tank of a washing tank or stabilization tank composed of three or more layers. It is preferable to process it.

  The processing steps applied to the processing method of the present invention are mainly composed of at least a color development step, a bleach-fixing step, a water washing step or a stabilization step, and subsequent drying, and in particular, a silver halide color light-sensitive material. As the developing process, an automatic developing machine is used.

  The automatic processor 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 process having a bleach-fixing processing tank, a water-washing process having a water-washing tank, or a stabilization process having a stabilization tank. Among them, a washing process having a washing tank or a stabilization process having a stabilization tank is composed of three or more treatment tanks, and the multi-stage direction for bringing the overflow liquid of each treatment tank into the treatment bath of the prebath One of the features is the flow method.

  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.

  The automatic developing machine 8 develops the 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 silver halide color photosensitive material P. As a processing solution container for storing a processing solution to be brought into contact with the silver halide color photosensitive material P, a plurality of liquid tanks 1 and an auxiliary tank 2 connected to the liquid tank 1 are provided side by side as shown below. ing. 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. In order to desilver (hereinafter also referred to as a bleach-fixing process) a certain color developing tank 1A and a color developing auxiliary tank 2A and a color developed silver halide color photosensitive material P, the silver halide color photosensitive material P is used. In order to wash or stabilize the bleach-fixing tank 1B and the bleach-fixing auxiliary tank 2B, which are part of the bleach-fixing solution container for storing the bleach-fixing solution to be contacted, and the bleach-fixed silver halide color photosensitive material P, Stabilization tank which is a part of a plurality of water washing or stabilizing solution containers connected in a multi-stage countercurrent system for storing washing water or stabilizing solution to be brought into contact with the silver halide color photosensitive material P C, 1D, 1E and stabilization auxiliary tanks 2C, 2D, 2E, and further, a drying unit 6 for drying the stabilized silver halide color photosensitive material P, and drying in the drying unit 6 The silver halide color photosensitive material P is fed 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 treatment method comprising the treatment steps as shown in FIG. 1, in the present invention, at least one of the washing tank or the stabilization tank has an ozone generator, and the ozonized bubbles are removed from the washing tank or the stabilization tank. It is characterized by being generated in a chemical bath and processed.

  In the treatment method of the present invention, by performing continuous treatment while generating ozonated bubbles in the washing tank or stabilization tank, generation of scales or the like adhering to the wall surface of the washing tank or stabilization tank, the transport roller, etc. In addition to promoting the decomposition of colorants such as sensitizing dyes and dyes that have flowed into the processing solution, washing water and stabilizing solution brought from the previous bath (bleach-fixing solution) by carry-over, and silver halide The white background characteristics can be drastically improved by accelerating the decomposition of sensitizing dyes and dyes remaining in the color light-sensitive material.

  In the present invention, the ozonized bubbles generated by the ozone generator are introduced into a washing tank or a stabilization tank for treatment.

  Examples of the ozone generator according to the present invention include a method of directly electrolyzing water, a silent discharge method, an electrolysis method or a method of generating ozone gas by an ultraviolet lamp method, but any type of ozone generator may be used, Among these, the method of blowing in ozone gas generated by the silent discharge method is preferable because high-concentration ozone water can be obtained at low cost.

  The capacity of the ozone generator is 0.1 g / hr to 20 g / hr, preferably about 0.5 g / hr to 10 g / hr, and ceramics from Sakura Co., Ltd., Simon Co., etc. are used. Inexpensive products are on sale. In order to effectively increase the concentration of ozone in the liquid, the raw material air should be as dry as possible, and preferably pressurized with a compressor.

  As an ozone generator, one using dry air as a raw material is advantageous in terms of cost, but the raw material may be taken from an oxygen cylinder. Also, there is a method obtained by electrolysis of water as described above, but since hydrogen is generated from the cathode, its recovery means is necessary, which is not preferable.

  A commercially available apparatus can be used as an ozone gas production apparatus, such as “D-OZONE Super 500” (manufactured by Shinko Plant Construction Co., Ltd.), “Ozex Water FZW”, and “Ozex Water ZW” (manufactured by Loki Engi Co., Ltd.). Etc.

  The ozone according to the present invention is preferably introduced as a fine bubble of ozone when it is introduced into the washing tank or the stabilization tank, via a nozzle (distributor) provided in the washing tank or the stabilization tank, or a porous member. And bubbling is preferred. The size of the fine ozone bubbles is preferably an average gas diameter of 0.02 to 10 μm.

  The ozone concentration in the washing water or the stabilizing solution according to the present invention is not particularly limited, but is in the range of 0.005 ppm to 100 ppm in consideration of corrosion and sterilizing power on materials such as treatment tanks and piping. The range of 0.01 ppm to 50 ppm is preferable.

  In addition, since ozone is highly toxic, the airtightness of the washing tank or stabilization tank should be increased as much as possible, and the ozone gas released from the surface of the treatment liquid must be reduced in concentration before being released outside the system. It is preferable to pass through an ozone adsorption filter containing an ozone adsorbing substance such as activated carbon, porous resin or porous silica, or a decomposition catalyst such as iron powder or MnO2.

  In addition, it is necessary to use a component having high ozone resistance for constituent members that come into contact with ozone, such as a processing tank, a pipe, a filter cartridge, a nozzle for discharging ozone gas, etc. constituting the washing tank or the stabilization tank according to the present invention. Yes, preferably stainless steel (SUS304, SUS317, etc.), titanium, aluminum, chromium, nickel, Teflon (registered trademark), silicon, vinyl chloride, pieton (fluoro rubber), ethylene / propylene rubber, silicon rubber, urethane rubber, glass, Particularly preferred are stainless steel, titanium, Teflon (registered trademark), and paiton.

  Further, in order to further enhance the sterilization effect, the washing tank or the stabilization tank according to the present invention is used in combination with an ultraviolet irradiation device, or a conventionally known disinfectant or antifungal agent is added to the washing water or the stabilizing liquid. You may use together.

  Next, a treatment method using the ozone generator according to the present invention will be specifically described with reference to the drawings.

  FIG. 2 is a schematic cross-sectional view showing an example of a stabilization treatment tank provided with an ozone generator, and is a cross-sectional view seen from the side of the stabilization tank (final tank) 1E shown in FIG.

  In FIG. 2, the silver halide color photosensitive material P is conveyed from the bottom of the drawing to the stabilization tank 1E while being held by the conveyance roller 11 and the support roller 12, and the stabilization process is performed.

  An ozonized bubble generator is provided on the side surface of the stabilization tank. After oxygen is taken in from air or an oxygen cylinder from C and pressurized by the compressor 15, oxygen is supplied to the ozone generator 5 to generate ozone gas. At this time, before sending the air to the compressor 15, a filter 16 is provided to remove foreign matter in the atmosphere and to prevent the ozone gas generated by the ozone generator 5 from flowing out into the atmosphere due to the backflow. The filter 16 preferably has a foreign matter removing function and an ozone adsorption function. For example, the filter 16 is made of a plastic sintered filter, a synthetic fiber filter, a foamed plastic filter, a ceramic filter, or the like, and contains the ozone decomposing substance. Or it is preferable to have a parallel structure, and two ozone adsorption / decomposition filters and foreign matter filters may be provided separately.

  The ozone gas generated by the ozone generator 5 is supplied from the distributor 13 to the stabilizing liquid as an ozonized gas having an average gas diameter of 0.02 to 10 μm while controlling the supply amount to the stabilization tank by the electromagnetic valve 14. Released. A part of the released ozone gas is dissolved in the stabilizing liquid, but most of the ozone gas floats and is released to the upper space from the surface of the stabilizing liquid. In consideration of safety, the released ozone gas passes through an ozone adsorption filter 18 filled with an ozone adsorbing substance by a pump 17 from a thin tube provided in the upper part of the stabilization treatment tank, and the ozone concentration is reduced to a safe region concentration. After the reduction, the three-way valve 20 is operated to release to the atmosphere via the path A, or to the ozone discharge device 5 again via the path B.

  In addition, on the opposite side surface of the stabilization tank, the stabilizing liquid is circulated by the circulation pump 23 for the purpose of achieving uniform processing, but regarding the filter 22 provided in the flow path of the pipe 21, Like the filter 16, it is preferable to have a foreign matter removing function and an ozone adsorption function.

  Further, in the treatment method of the present invention, the ozonized bubbles are introduced using the above-described ozone generator, and electrolyzed water (hereinafter also referred to as electrolyzed water) is used as washing water or a stabilizing liquid. It is preferable to use electrolyzed water as washing water or a stabilizing solution to obtain a more excellent white background characteristic which is the object effect of the present invention.

  The electrolysis treatment used in the present invention is, for example, a method in which an electrolytic layer is divided into an anode and a cathode by a diaphragm, or a non-diaphragm flowing water type or a batch type and is performed between an anode and a cathode. It refers to treating water by energizing an electric current. Since water contains a small amount of electrolyte such as sodium chloride or potassium chloride, water obtained by electrolysis with a weak direct current is preferable. It is also preferable to subject general tap water to electrolytic treatment.

  For example, electrolyzed water can be obtained by treating tap water under the following electrolysis conditions. In the present invention, this electrolyzed water is used for the preparation of a stabilizing solution or a stabilizing replenisher.

(Electrolysis conditions)
Battery voltage about 2.2V / cell (constant voltage, equal to 0.8Vvs.SCE)
Current density about 0.25 A / dm
Current density approx. 0.83A / l
LV value (linear velocity) approx. 0.80cm / sec
FIG. 3 shows a sectional view of the structure of the electrolytic treatment tank used.

  A (−) terminal electrode 102 and a (+) terminal electrode 103 are installed inside the electrolytic treatment tank 101 shown in FIG. 3, and a liquid to be subjected to electrolytic treatment enters from the inlet 104, and electrolytic water flows from the outlet 105. It has a structure to go out.

  FIG. 4 shows a configuration diagram including a peripheral device for producing the electrolyzed water 110 in the electrolytic treatment tank 101. In FIG. 4, 111 is a DC power source, 112 is a filter, 113 is a pump, and 114 is an electrolyte bath.

  Next, each processing solution used in the processing method of the present invention will be described.

  First, the color development process will be described.

  A known aromatic primary amine developing agent can be used in the color developer according to the present invention. Examples of these compounds include the following compounds.

CD-1: N, N-diethyl-p-phenylenediamine CD-2: 2-amino-5-diethylaminotoluene CD-3: 2-amino-5- (N-ethyl-N-laurylamino) toluene CD-4 : 4- (N-ethyl-N- (β-hydroxyethyl) amino) aniline CD-5: 2-methyl-4- (N-ethyl-N- (β-hydroxyethyl) amino) aniline CD-6: 4 -Amino-3-methyl-N-ethyl-N- (β- (methanesulfonamido) ethyl) -aniline CD-7: N- (2-amino-5-diethylaminophenylethyl) methanesulfonamide CD-8: N , N-dimethyl-p-phenylenediamine CD-9: 4-amino-3-methyl-N-ethyl-N-methoxyethylaniline CD-10: 4-amino-3-methyl-N Ethyl-N- (β-ethoxyethyl) aniline CD-11: 4-amino-3-methyl-N-ethyl-N- (γ-hydroxypropyl) aniline In the color developer used in the present invention, a color developing agent is used. In order to reduce disappearance due to oxidation, it is preferable to contain a preservative. Representative preservatives include hydroxylamine derivatives. Examples of the hydroxylamine derivatives that can be used in the present invention include hydroxylamine salts such as hydroxylamine sulfate and hydroxylamine hydrochloride, as well as JP-A-1-97953, 1-186939, 1-186940, Hydroxylamine derivatives described in, for example, 1-1875557 can be used.

  Other preservatives include hydroxamic acids, hydrazides, phenols, α-hydroxy ketones, α-amino ketones, saccharides, monoamines, diamines, polyamines, quaternary ammonium salts, nitroxy radicals. , Alcohols, oximes, diamide compounds, and condensed amines. 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, US Pat. Nos. 3,615,503, 2,494,903, JP-A-52. -1433020, Japanese Patent Publication No. 4830696 and the like.

  In addition, various metals described in JP-A-57-44148 and JP-A-57-53749, salicylic acids described in JP-A-59-180588, triethanolamine, and triisopananolamine The alkanolamines described in US Pat. No. 54-3532, aromatic polyhydroxy compounds described in US Pat. No. 3,746,544 and the like may be contained as necessary.

  The color developer used in the present invention is preferably 9.0 or more and 13.5 or less, more preferably 9.5 or more and 12.0 or less, and an alkaline agent and a buffer so that the pH value can be maintained. Agents and optionally acids can be included.

  From the viewpoint of maintaining the pH when the color developing solution is prepared, the following buffering agent is 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-propandiol salt, valine salt, proline salt, trishydroquinaminomethane 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 10.0 or higher, and even when added to a color developer, they adversely affect photographic performance (capriformation). Etc.) and a preferable buffer from the viewpoint of being inexpensive.

  Exemplary compounds of the buffer include sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, disodium phosphate, dipotassium phosphate, sodium borate, potassium borate , Sodium tetraborate (borax), potassium tetraborate, sodium o-hydroxybenzoate (sodium salicylate), potassium o-hydroxybenzoate, sodium 5-sulfo-2-hydroxybenzoate (sodium 5-sulfosalicylate) And potassium 5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate). However, the present invention is not limited to these compounds.

  These buffers are preferably 0.01 to 2 mol, more preferably 0.1 to 0.5 mol, per liter of color developer.

  As the other components, for example, calcium and magnesium precipitation inhibitors and various chelating agents which are also stability improvers can be added to the color developer used in the present invention. For example, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, ethylenediaminetetraacetic acid, N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N, N ′, N′-tetramethylenesulfonic acid, transsirohexasidiaminetetraacetic acid, 1,2-diaminopropan tetraacetic 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 -Dihydroxybenzene-4,6-disulfonic acid and the like It is. These chelating agents may be used in combination of two or more as required. Further, the amount of these chelating agents may be an amount sufficient to sequester metal ions during color developer processing. For example, 0. 1 per liter. It is added so as to be about 1 to 10 g.

  If necessary, an arbitrary development accelerator can be added to the color developer used in 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 thioether compounds represented in the specification, p-phenylenediamine compounds represented in JP-A-52-49829 and JP-A-50-15554, JP-A-50-137726, JP-B-44-30074 Quaternary ammonium salts represented in JP-A-56-156826 and JP-A-52-43429, U.S. Pat. Nos. 2,494,903, 3,128,182 and 4,230,796. 3,253,919, Japanese Patent Publication No. 41-11431, U.S. Pat. Nos. 2,482,546, 2,596,926, and 3,582,346, etc. Amine compounds described in the report or specification, Japanese Patent Publication No. 37-16088, Japanese Patent Publication No. 42-25201, US Pat. No. 3,128,183, Japanese Patent Publication No. 41-11431, Japanese Patent Publication No. 42-23883, and US Pat. Polyalkylene oxide, other 1-phenyl-3-virazolitones or imidazoles represented in each publication or specification such as 3,532,501 can be added as necessary. Their concentration is preferably 0.001 to 0.2 mol, more preferably 0.01 to 0.05 mol, per liter of the color developer.

  In addition to halogen ions, an optional antifoggant can be added to the color developer as required. Examples of organic antifoggants include benzotriazole, 6-nitrobenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chloro-benzotriazole, 2-thiazolyl-benzimidazole, 2 -Nitrogen-containing heterocyclic compounds such as thiazolylmethyl-benzimidazole, indazole, hydroxyazaindolizine, and adenine are typical examples.

  In addition, a fluorescent whitening agent can be used in the color developer used in the present invention, if necessary. As the optical brightener, a bis (triazinylamino) stilbene sulfonic acid compound is preferred. As the bis (triazinylamino) stilbene sulfonic acid compound, a known or commercially available diaminostilbene-based auto-enhancing agent 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.

  Other bis (triazinylamino) stilbene sulfonic acid compounds include compounds I-1 to I-48 and paragraphs [0038] to [0049] described in paragraphs [0038] to [0049] of JP-A No. 2001-281823. The compounds II-1 to II-16 described in paragraph Nos. [0050] to [0052] of JP-A-281823 can also be mentioned. The addition amount of the above-described optical brightener is preferably 0.1 to 0.1 mol per liter of color developer.

  The temperature of the color developer used in the color development step according to the present invention is preferably high in terms of simply increasing the image density obtained, but there is also a problem with the stability of the color developer itself, and the temperature is excessively high. If set, it may be a factor that degrades image stability. Accordingly, the temperature of the color developer is preferably 40 ° C. or lower, more preferably 38 ° C. or lower.

  Next, details of the bleach-fixing step according to the present invention will be described.

  In the present invention, any bleaching agent can be used as a bleaching agent used in the bleach-fixing solution, and in particular, an organic complex salt of iron (III) (for example, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, nitrilotriacetic acid, cyclohexanediamine). Aminopolycarboxylic acids such as tetraacetic acid and ethylenediaminedisuccinic acid, complex salts such as aminopolyphosphonic acid, phosphonocarboxylic acid and organic phosphonic acid) or organic acids such as citric acid, tartaric acid and malic acid; persulfates; Hydrogen and the like are preferable.

  Of these, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, 1,3-diaminopropanetetraacetic acid, ethylenediaminedisuccinic acid, and iron (III) complex salt of methyliminodiacetic acid are preferred because of their high bleaching power. 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. A ferric ion complex salt may be formed in a solution using iron or the like and a chelating agent such as aminopolycarboxylic acid, aminopolyphosphonic acid, or phosphonocarboxylic acid. Moreover, you may use a chelating agent in excess rather than forming a ferric ion complex salt. Among the iron complexes, aminopolycarboxylic acid iron complexes are preferable, and the addition amount is preferably 0.01 to 1.0 mol / liter, more preferably 0.05 to 0.50 mol / liter.

  Various compounds can be used as a bleaching accelerator in the bleach-fixing solution. For example, a compound having a mercapto group or a disulfide bond described in Research Disclosure No. 17129 (July 1978), a thiourea compound, or a halide such as iodine or bromine ion is preferable in terms of excellent bleaching power.

  In addition, the bleach-fixing solution may contain a rehalogenating agent such as bromide (for example, potassium bromide) or chloride (for example, potassium chloride) or iodide (for example, ammonium iodide). One or more inorganic acids with pH buffering capacity such as borax, sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, citric acid, sodium citrate, tartaric acid, succinic acid, maleic acid, glycolic acid Organic acids and their alkali metal or ammonium salts, or corrosion inhibitors such as ammonium nitrate and guanidine can be added.

  Fixing agents used in the bleach-fixing solution are known fixing agents, that is, thiosulfates such as sodium thiosulfate and ammonium thiosulfate; thiocyanates such as sodium thiocyanate and ammonium thiocyanate; ethylenebisthioglycolic acid, 3, These are water-soluble silver halide solubilizers such as thioether compounds such as 6-dithia-1,8-octanediol and thioureas, and these can be used alone or in combination. In the present invention, it is preferable to use thiosulfuric acid, particularly ammonium thiosulfate. The amount of the fixing agent per liter is preferably from 0.1 to 5.0 mol, more preferably from 0.3 to 2.0 mol.

  Bleach fixers may contain sulfites such as sodium sulfite, potassium sulfite, ammonium sulfite, potassium bisulfite, sodium bisulfite, sodium metabisulfite, potassium metabisulfite, ammonium metabisulfite as preservatives. In general, ascorbic acid, a carbonyl bisulfite adduct, a carbonyl compound, or the like may be added. Furthermore, you may add a buffering agent, a fluorescent whitening agent, a chelating agent, an antifoamer, an antifungal agent, etc. as needed.

  In the present invention, in order to increase the activity of the bleach-fixing solution, air or oxygen may be optionally blown in the processing bath and in the processing replenisher storage tank, or a suitable oxidizing agent such as peroxidation may be used. Hydrogen, bromate, persulfate, or the like may be added as appropriate.

  The pH of the bleach-fixing solution is preferably 5.0 to 9.0, more preferably 5.5 to 8.0. The pH of the bleach-fixing solution is the pH of the processing tank at the time of processing the photosensitive material, and not the pH of the replenishing solution.

The time required for the bleach-fixing step applied to the processing method of the present invention is preferably 90 seconds or less, more preferably 45 seconds or less. The time required for the bleach-fixing step here refers to the time from when the photosensitive material is immersed in the first tank until it leaves the final tank when the process has a plurality of tanks. It refers to the time until the photosensitive material is immersed in the subsequent washing solution or stabilizing solution, and includes the crossover time therebetween. The crossover time is preferably 10 seconds or less, more preferably 5 seconds or less. Also. The temperature of the bleach-fixing solution is preferably 20 to 70 ° C, and desirably 25 to 50 ° C. Further, the replenishment rate of the bleach-fixing solution is preferably 200 ml / m ² or less, and more preferably ^{20ml / m 2 ~100ml / m 2} .

The replenishment amount of the bleaching solution is preferably 200 ml / m ² or less, more preferably 150 ml / m ² or less from the viewpoint of further achieving the object effect of the present invention, and particularly 50 ml / m ^{2 to} 150 ml / m ^2. It is preferable that

  Further, the temperature of the bleach-fixing solution used in the bleach-fixing step is preferably high in terms of simply improving the bleach-fixing ability and improving the white background, but like the color developer, the bleach-fixing solution itself has a preserving property. From the problem, it is preferably 43 ° C. or lower, more preferably 40 ° C. or lower.

  Next, the stabilizing solution will be described.

  It is particularly preferred for the purposes of the present invention that the stabilizer 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 from 0.01 to 50 g, and more preferably from 0.05 to 20 g, per liter of the stabilizing solution.

  Moreover, an ammonium compound is mentioned as a preferable compound added to a stabilizer. 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 amount of ammonium compound added 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 stabilizer.

Furthermore, it is preferable that the stabilizer contains sulfite. 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 in an amount of at least 1 × 10 ⁻³ mol / liter, more preferably 5 × 10 ⁻³ mol / liter to 10 ⁻¹ mol / liter, in the stabilizer. Such an amount is added, and has an effect of preventing stains in particular. 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 stabilizers include polyvinylpyrrolidone (PVP K-15, K-30, K-90), organic acid salts (citric acid, acetic acid, succinic acid, oxalic acid, benzoic acid). Acid), 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 agents known as pulp industry slime control agents) or optical brighteners, surfactants, preservatives, metal salts such as Bi, Mg, Zn, Ni, Al, Sn, Ti, Zr, etc. is there. 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, and still more preferably The range is 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 replenisher, or they 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 stabilizer (tank solution) by adhering it to the photosensitive material to be processed from the pre-bath and bringing it in.

  Further, in the present invention, a stabilizing solution in which calcium ion and magnesium ion 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-mentioned antibacterial agent or halogen ion releasing compound. It 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.

  One of the characteristics of the present invention is that the treatment temperature during the stabilization treatment or the water washing treatment is 40 ° C. or more in the first tank, but other than that, 15 ° C. to 70 ° C. is preferable, and more preferably 20 ° C. to It is in the range of 55 ° C. In particular, the temperature of the liquid in the total stabilization treatment tank or the washing tank is preferably 40 ° C. or higher. The treatment time for the stabilization treatment or the water washing treatment is preferably 120 seconds or less.

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

In the present invention, the washing or stabilizing solution is also characterized in that it contains only additives such as scale inhibitor, 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.

  The development processing apparatus used for the development processing of the silver halide photosensitive material of the present invention fixes the photosensitive material to the belt even if it is a roller transport type that conveys the photosensitive material between rollers arranged in a processing tank. The endless belt method may be used, but the processing tank is formed in a slit shape, the processing liquid is supplied to the processing tank, and the photosensitive material is transported and the processing liquid is sprayed. Also, a web system by contact with a carrier impregnated with a treatment liquid, a system by a viscous treatment liquid, or the like can be used. In the case of processing in large quantities, a running process is usually performed using an automatic processor. At this time, the replenishment amount of the replenisher is preferably as small as possible, and the most preferable processing form in view of environmental suitability is the tablet as a replenishment method. And the method described in the published technical report 94-16935 is most preferable.

  In addition, a semicircular guide made of a material such as plastic or Teflon (registered trademark) with a low surface slip resistance is arranged at the transition portion provided between the treatment tanks, thereby efficiently on the liquid surface. A method of carrying a U-turn to convey a photosensitive material is also generally used.

  Further, in the drying process, particularly in the case of an automatic developing machine for a photosensitive material having a large size of A3 or larger, the photosensitive material is conveyed by driven opposing rollers provided at the entrance and exit portions of the photosensitive material. In the case of the wind drying method, generally, a plurality of elongated bars such as piano wires are arranged on the upper and lower surfaces or the lower surface of the photosensitive material inside the unit, and the photosensitive material is designed to slide there. All of these guides are arranged in parallel to the conveyance direction of the photosensitive material. However, it is preferable to arrange the guides at a slight angle in the conveyance direction so that the photosensitive material can be conveyed more smoothly. A preferred angle is 3 ° or more and 20 ° or less. More preferably, it is 3 ° or more and 10 ° or less. As the direction in which the angle is given, an arrangement is preferred in which each is directed outward from the center in the transport direction.

  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.

  Next, a method for forming an image of the silver halide color light-sensitive material according to the present invention will be described.

  As the exposure light source of the exposure apparatus used in the present invention, any known light source can be preferably used, but a laser or a light emitting diode (hereinafter referred to as LED) is more preferably used.

  As the laser, a semiconductor laser (hereinafter referred to as LD) is preferably used because it is compact and has a long light source life. LDs are used for applications such as DVDs, optical pickups for music CDs, barcode scanners for POS systems, optical communications, etc., and they are inexpensive and can provide relatively high output. have. Specific examples of the LD include aluminum, gallium, indium, arsenic (650 nm), indium, gallium, phosphorus (up to 700 nm), gallium, arsenic, phosphorus (610-900 nm), gallium, aluminum, arsenic (760-850 nm). And the like. Recently, a laser that oscillates blue light has been developed. However, at present, it is advantageous to use an LD as a light source having a wavelength longer than 610 nm.

  As a laser light source having an SHG element, light emitted from an LD or YAG laser is converted to a half-wavelength light by an SHG element and emitted, and since visible light is obtained, there is no green light source. ~ Used as a light source in the blue region. An example of this type of light source is a YAG laser combined with an SHG element (532 nm).

  Examples of the gas laser include a helium / cadmium laser (about 442 nm), an argon ion laser (about 514 nm), a helium neon laser (about 544 nm and 633 nm), and the like.

  LEDs having the same composition as LD are known, but various LEDs from blue to infrared have been put into practical use.

  As the exposure light source used in the present invention, each laser may be used alone, or may be used in combination as a multi-beam. In the case of an LD, for example, a beam composed of 10 luminous fluxes can be obtained by arranging 10 LDs. On the other hand, in the case of a helium neon laser, light emitted from the laser is divided into, for example, 10 light beams by a beam separator.

  The intensity change of the exposure light source can be directly modulated to change the value of the current flowing through each element in the case of an LD or LED. In the case of an LD, the intensity may be changed using an element such as an AOM (acousto-optic modulator). In the case of a gas laser, it is common to use devices such as AOM and EOM (electro-optic modulator).

  When an LED is used as the light source, a method of exposing the same pixel with a plurality of elements may be used as long as the amount of light is weak.

  Moreover, you may use an organic light emitting element as a light source which replaces these, These are described in Unexamined-Japanese-Patent No. 2000-258846 etc., for example.

  The emission wavelength of the light source can be preferably used in any wavelength region where the photosensitive material has sufficient sensitivity, but it has a sufficient sensitivity difference with other photosensitive layers in order to prevent color turbidity. It is preferable to use a region. Although it depends on the contrast of the photosensitive material, it is preferable that the common logarithm of the exposure amount has a sensitivity difference of 0.6 or more, preferably 1.0 or more. In addition, when the emission wavelength varies depending on the environmental conditions and operating conditions in which the light source is placed, it is theoretically preferable to match the peak wavelength of the spectral sensitivity. It is preferable to select the wavelength in consideration of the relationship. Examples thereof include JP-A-6-75342 and JP-A-2001-83663. Further, when not only the emission wavelength but also the emission intensity varies, it is preferable to select the emission wavelength in relation to the spectral sensitivity. Examples thereof include Japanese Patent Application Laid-Open No. 2002-72367 and Nikkei New Material September 1987. It is described on page 54 of the 14th of the month.

  In the present invention, the term area gradation image is used, but this is not expressed by the shading of the color of each pixel, but by the size of the area of the color developed at a specific density. It can be considered synonymous with halftone dots.

  Usually, in the case of area gradation exposure, the purpose can be achieved by causing Y, M, C, and black to be colored. More preferably, in order to identify that a single color such as M or C has developed in addition to black, it is preferable to perform exposure using different exposure amounts of three or more values. In printing, a special color plate may be used, but in order to reproduce this, it is preferable to perform exposure using different exposure values of four or more values.

  In the case of a laser light source, the beam diameter is preferably 25 μm or less, more preferably 6 to 22 μm. If it is smaller than 6 μm, it is preferable in terms of image quality, but adjustment is difficult or the processing speed decreases. On the other hand, if it is larger than 25 μm, unevenness increases and the sharpness of the image also deteriorates. By optimizing the beam diameter, high-definition images without unevenness can be written at high speed.

  In order to draw an image with such light, it is necessary to scan the silver halide color photosensitive material with a light beam. The silver halide color photosensitive material is wound around a cylindrical drum and rotated while rotating at high speed. A so-called cylindrical outer surface scanning method in which a light beam is moved in a direction perpendicular to the direction may be employed, and a so-called cylindrical inner surface scanning method in which a silver halide color photosensitive material is exposed in close contact with a cylindrical depression may be preferably used. A so-called plane scanning method may be employed in which the polyhedral mirror is rotated at a high speed, and the silver halide color photosensitive material conveyed thereby is exposed by moving the light beam perpendicular to the conveying direction. From the viewpoint of high image quality and obtaining a large image, the cylindrical outer surface scanning method is more preferably used.

  In order to perform exposure by the cylindrical outer surface scanning method, the silver halide color photosensitive material must be brought into close contact with the cylindrical drum accurately. In order to reliably perform this close contact, it is necessary to accurately align and transport. The silver halide color light-sensitive material used in the present invention can be preferably used because the surface on the side to be exposed (the side on which the silver halide emulsion layer is coated) can be more accurately aligned. From the same viewpoint, the support used for the silver halide color photographic material used in the present invention has an appropriate rigidity, and a Taber rigidity of 0.8 to 4.0 is preferable.

  The diameter of the exposure drum can be arbitrarily set according to the size of the silver halide color photosensitive material to be exposed. The number of rotations of the exposure drum can be arbitrarily set, but an appropriate number of rotations can be selected depending on the beam diameter of the laser beam, the energy intensity, the writing pattern, the sensitivity of the silver halide color photosensitive material, and the like. From the viewpoint of productivity, it is preferable that scanning exposure can be performed at a higher rotation speed. Specifically, 200 to 3000 rotations per minute is preferably used.

  The silver halide color photosensitive material can be fixed to the exposure drum by mechanical means, or a large number of fine holes that can be sucked on the drum surface are provided according to the size of the silver halide color photosensitive material. In addition, the silver halide color light-sensitive material can be attracted and adhered. Adhering the silver halide color photosensitive material to the exposure drum as much as possible is important to prevent troubles such as image unevenness.

  As an apparatus used for image formation, a system in which a plurality of photosensitive materials are set in advance and a silver halide color photosensitive material is appropriately selected and used can be preferably used. In this case, the two types of silver halide color light-sensitive materials may be, for example, silver halide color light-sensitive materials having different widths, or silver halide color light-sensitive materials having different surface properties (unevenness of the support). Can do. The silver halide color light-sensitive material may be selected by a method that is set by a switch of an image forming apparatus or the like, or setting information may be transmitted together with image data and selected based on the setting information. It can also be advantageously used to automatically select the optimum size of the silver halide color photosensitive material according to the size of the image data. In special cases, the same type of silver halide color photosensitive material is loaded, and when one silver halide color photosensitive material is used up, the other silver halide color photosensitive material is automatically used. This can be used advantageously because continuous unmanned operation is possible.

  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 produce 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"
Each of the above prepared samples 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 facing outward. Then, a light-shielding sheet 6 cm wide was attached, and it was further wound three times, and fixed so as not to loosen.

  Each of the roll samples thus prepared 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.

Image data includes yellow (Y), magenta (M), cyan (C), and black (K) colors 3, 5, 10, 20, 30, 40, 50, 60, 70, 80, 90, and 95. 100% dot test chart was used. A square pattern of 5 cm square was used for each halftone dot%. The size of the photosensitive material used was 670 mm (width) × 970 mm (length), the halftone dots were halftone dots formed by the AM screen method, and the number of halftone dots of 30% was 20 × 10 ³ pieces / inch ^2. It was. Note that 1 inch is 2.54 cm.

  The exposure light source uses LEDs for all of R, G, and B, and the center wavelengths when driving at 20 mA are B: 454 to 462 nm, G: 520 to 536 nm, and R: 646 to 670 nm, respectively. Multi-beam. The light intensity modulation resolution was 1024 gradations, and the light intensity modulation response was within 200 nanoseconds. The amount of exposure was adjusted so that the solid image with the halftone dot of 100% had the smallest color difference from its target. As targets, 100% each of Y, M, C, and K of the Japan Printing Industrial Machinery Manufacturers Association, created by the ISO / TC130 National Committee, Japan Color color reproduction printing 2001, art paper, and ISO12647 pattern were used.

  The drum surface reflectance was 5% on average in the region of 350 nm to 800 nm, and the arithmetic surface height was 4.0 μm. The exposure was performed at a drum rotation speed of 1000 revolutions per minute.

  After the exposure was completed and the rotation of the drum was stopped, an operation of peeling each sample as a silver halide color photosensitive material from the drum was performed.

<Development processing>
About each produced said sample, it was made to convey to an automatic processor and the following each development processing was performed. 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 until the replenishment amount of the color developer reached twice the amount of the color development tank (21.1 L) (hereinafter referred to as 2 rounds).

[Treatment method A]
(Processing conditions)
Processing process Processing temperature Processing time Processing tank capacity Replenishment amount
(° C) (seconds) (L) (ml / m ² )
Color development 41.0 ± 0.3 118 21.1 275
Bleach fixing 38.0 ± 0.5 52 9.0 155
Stabilization 1 Result 36 6.0 * 1
Stabilization 2 37.0 ± 1.0 36 6.0 * 2
Stabilization 3 Result 32 6.0 330
Dry 55-65 ° C. 37
* 1) Cascade flow from Stabilization 2 to Stabilization 1 * 2) Cascade flow from Stabilization 3 to Stabilization 2 The processing time is the following after the tip of the sample enters the tank. It shall represent the time to enter the tank.

  The stabilization process was a multi-stage counter-current system in which the stabilizing replenisher was replenished in the third tank with the replenishment amount of the stabilizing liquid, sequentially overflowing the second tank and the first tank, and flowing out from the first tank as waste liquid. The drying unit installed a pair of rollers at the entrance and the exit, respectively, and transported the photosensitive material in the horizontal direction by driving them. The hot air unit was dried by spraying from the upper surface of the photosensitive material. Between the entrance and exit rollers, a piano wire having a diameter of 3 mm wound with a Teflon (registered trademark) seal is placed in parallel with the conveyance direction of the photosensitive material, 10 pieces above and below the path through which the photosensitive material passes at random intervals. The photosensitive material was made to slide in the direction.

(Each treatment composition)
<Preparation of color developer>
Tank liquid Replenisher Pure water 800ml 800ml
Triethylenediamine 2g 3g
Diethylene glycol 10g 10g
Potassium bromide 0.01g −
Potassium chloride 3.5g −
Potassium sulfite 0.25g 0.5g
N-ethyl-N- (2-hydroxyethyl) -4-aminoaniline, 3/2 sulfate, monohydrate 4.2 g 6.9 g
N, N-disulfoethylhydroxylamine 20.4 g 18.0 g
Triethanolamine 10.0 g 10.0 g
Diethylenetriaminepentaacetic acid sodium salt 2.0 g 2.0 g
Optical brightener (4,4'-diaminostilbene disulfonic acid derivative)
2.0g 2.5g
Potassium carbonate 30g 30g
Water was added to a total volume of 1 liter, the tank solution was adjusted to pH 10.0 and the replenisher solution was adjusted to pH 10.6 using 50% sulfuric acid or potassium hydroxide.

<Preparation of bleach-fixing solution>
Tank liquid = replenisher pure water 800ml
65 g of diethylenetriaminepentaacetic acid ferric ammonium dihydrate
Diethylenetriaminepentaacetic acid 3g
Ammonium thiosulfate (70% aqueous solution) 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.

<Preparation of stabilizing solution>
Tank liquid = replenisher pure water 900ml
o-Phenylphenol 1.0g
5-Chloro-2-methyl-4-isothiazolin-3-one 0.02 g
2-Methyl-4-isothiazolin-3-one 0.02 g
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 bring the total volume to 1 liter, and the pH was adjusted to 7.5 with sulfuric acid or aqueous ammonia.

[Processing method B]
In the above processing method A, the same thing except that the ozonized bubbles were supplied to the first stabilization tank of stabilization 1 using the ozone generator shown in FIGS. 1 and 2 so that the ozonated bubbles hit the entire surface of the silver halide color photosensitive material. Thus, this was designated as Processing Method B. The ozone gas supply amount was controlled so that the ozone concentration at this time was 0.01 ppm.

[Process C]
In the processing method A, the ozone generator shown in FIGS. 1 and 2 is used in the third stabilization tank of stabilization 3 (final tank) so that the ozonated bubbles hit the entire surface of the silver halide color photosensitive material. In the same manner as described above, this was designated as processing method B. The ozone gas supply amount was controlled so that the ozone concentration at this time was 0.01 ppm.

[Processing method D]
In the above processing method A, the ozone generators shown in FIGS. 1 and 2 were used in all stabilization tanks of stabilization 1 to stabilization 3 so that the ozonated bubbles hit the entire surface of the silver halide color photosensitive material. This was treated in the same manner as the processing method B. The ozone gas supply amount was controlled so that the ozone concentration at this time was 0.01 ppm.

<Evaluation of characteristics>
[Evaluation of stability on white background]
For the above processing methods A to D, an unexposed silver halide color light-sensitive material having a size of 670 mm × 970 mm is processed immediately after the start of processing and when two or more rounds of continuous processing are performed, and the entire white background is 20 points × 30. The points were divided into a total of 600 points, the average value of the L ^* a ^* b ^* values of the 600 white points was determined, and the color difference ΔE was determined according to the following formula, which was used as a measure of the white background stability.

ΔE = [(ΔL ^* ) ² + (Δa ^* ) ² + (Δb ^* ) ² ] ^1/2
Here, ΔL ^* , Δa ^* , and Δb ^* represent differences immediately after the start of processing and after 2R continuous processing.

L ^* a ^* b ^* is measured using a spectrophotometric colorimeter CM-2022 manufactured by Konica Minolta Sensing Co., Ltd. and measured using a geometric condition d-0 for illumination and light reception and a xenon pulse light source. The value of L ^* a ^* b ^* at light D50 was calculated.

  Table 2 shows the evaluation results obtained as described above.

  As is clear from the results shown in Table 2, the treatment according to the present invention in which the stabilization tank is a three-stage multi-stage countercurrent system, and at least one of the stabilization tanks is processed by generating ozonated bubbles with an ozone generator. It can be seen that the method is superior in white background stability in continuous processing as compared to the comparative example.

Example 2
[Treatment methods A2 to D2]
In the processing method A~D described in Example 1, the replenishing amount of the stabilizing replenisher stabilization step, was changed from 330 ml / m ² to 215 ml / m ² in the same manner, prepared in Example 1 The silver halide color light-sensitive material thus obtained was subjected to continuous processing up to two rounds, which were designated as processing methods A2 to D2.

[Evaluation of stability on white background]
The white background stability was evaluated in the same manner as in the method described in Example 1, and the results obtained are shown in Table 3.

As is apparent from the results shown in Table 3, even in a low replenishment condition where the replenishment amount of the stabilizing liquid replenisher is 215 ml / m ² , the stabilizing tank is a three-stage multi-stage countercurrent system, and at least the stabilizing tank It can be seen that the treatment method of the present invention, in which one tank is treated by generating ozonated bubbles with an ozone generator, is superior to the comparative example in white background stability in continuous treatment.

Example 3
[Treatment methods A3 to D3]
In the processing methods A to D described in Example 1, preparation of the stabilizing solution and the replenishing solution in the stabilization step was performed in the same manner as in Example 1 except that electrolyzed water prepared by the following method was used. Using silver halide color light-sensitive material, continuous processing up to 2 rounds was performed, and this was designated as processing methods A3 to D3.

(Preparation of electrolyzed water)
The tap water was treated under the following electrolysis conditions using the electrolytic treatment tank shown in FIGS. 3 and 4 to prepare electrolyzed water.

<Electrolysis conditions>
Battery voltage about 2.2V / cell (constant voltage, equal to 0.8Vvs.SCE)
Current density about 0.25 A / dm
Current density approx. 0.83A / l
LV value (linear velocity) approx. 0.80cm / sec
[Evaluation of stability on white background]
The white background stability was evaluated in the same manner as in the method described in Example 1, and the results obtained are shown in Table 3.

  As is clear from the results shown in Table 4, the stabilization tank is a three-stage multi-stage countercurrent system, and at least one of the stabilization tanks is treated by generating ozonated bubbles with an ozone generator and stabilizing. The treatment method of the present invention using electrolyzed water for the preparation of the liquid is superior to the comparative example in white background stability in continuous treatment, and the white background stability is further improved compared to the method described in Example 1. I understand that

It is a schematic block diagram which shows an example of the image development processing part of the automatic processor which can be used by this invention. It is a schematic sectional drawing which shows an example of the stabilization processing tank provided with the ozone generator. It is a composition sectional view showing an example of an electrolysis processing tank used for preparation of electrolysis water. It is a block diagram including the peripheral device for preparing electrolyzed water in an electrolytic treatment tank.

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 3rd stability auxiliary tank 3A Replenishing color developer supplying unit 3B Replenishing bleach-fixing agent supplying unit 3E Replenishing stabilizer supplying unit 4 Photosensitive material transport unit 5 Ozone generator 6 Drying unit 8 Automatic developing machine P Silver halide color photosensitive material DESCRIPTION OF SYMBOLS 13 Distributor 15 Compressor 16,22 Filter 17,23 Pump 18 Ozone adsorption filter 23 Circulation pump O Ozonation bubble S Stabilization liquid 101 Electrolysis process tank 102 (-) Terminal electrode 103 (+) Terminal electrode 104 Inlet 105 Outlet 110 Electrolyzed water 111 DC power supply 112 Filter 113 Pump 114 Electricity Liquid tank

Claims (3)

In the processing method of a silver halide color photographic material in which the exposed silver halide color photographic material is processed through at least a color development step, a bleach-fixing step, a water washing step or a stabilization step, the water washing step or the stabilization step is performed. The water washing tank or stabilization tank to be constructed is a multi-stage countercurrent system having three or more layers, at least one of the water washing tank or the stabilization tank has an ozone generator, and the ozonized bubbles are removed from the water washing tank or the stability tank. A method for processing a silver halide color light-sensitive material, which is generated in a crystallization tank and processed. 2. The method for processing a silver halide color light-sensitive material according to claim 1, wherein the ozonized bubbles are generated and processed in a final tank of a washing tank or a stabilization tank composed of three or more layers. 3. The method for processing a silver halide color photographic material according to claim 1, wherein the water washing tank or the stabilization tank uses electrolyzed water.

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