JP2005316251A - Concentrated bleaching composition for silver halide color photographic sensitive material and processing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a concentrated bleach-fixing composition which ensures temporal stability, stability in use, bleach fogging resistance, elimination of the odor of acetic acid and silver recovery efficiency. <P>SOLUTION: The concentrated bleaching composition for a silver halide photosensitive material comprises a single solution which contains 0.10-0.42 mol/l of an iron (III) complex salt of ethylenediaminetetraacetic acid as a bleaching agent, 0.5-10 mol% of uncomplexed ethylenediaminetetraacetic acid based on the amount of the bleaching agent, and 0.10-0.40 mol/l of a dibasic acid having a pKa of 2.0-5.0, and has a pH of 2.0-3.5. A processing method for the silver halide color photographic sensitive material replenishes a bleach-fixing tank with the bleaching composition and a concentrated fixing composition containing 1.0-3.0 mol/l of a thiosulfate in a ratio of 1:1 and performs bleach-fixing in 10-30 s. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a liquid photographic processing agent for a silver halide color photographic light-sensitive material (hereinafter sometimes simply referred to as a light-sensitive material). In particular, the present invention relates to a bleach concentration processing composition, a bleach replenisher prepared therefrom, and a photographic processing method using the same.

  In recent years, automatic development processing machines called minilabs that are installed at the photographic store front and process photographic photosensitive materials have become widespread for quick service to general users and rationalization of collection and delivery between photographic stores and processing shops. . If the development processing agent for minilabs is in the form of a liquid composition in which constituent processing chemicals are previously dissolved in a solvent such as water, the processing solution can be prepared by simple preparation operations such as mixing and dilution with water before use. Therefore, it is often supplied in this form. However, the liquid composition form is disadvantageous in terms of transportation costs due to the large amount of water contained in the treatment liquid and the container for storing the composition. It is generally supplied in the form of a concentrated treatment composition (referred to in the industry as “concentration” instead of “concentration”. This “concentration” does not mean a thickening operation such as evaporation or dehydration). Is.

  Also, the liquid concentration processing agent for bleach-fixing contains a two-component composition that is more stable than a single-component composition, that is, a bleach-concentrated composition part containing a bleaching agent (hereinafter also referred to as a bleaching agent part) and a fixing agent. It is generally composed of two parts, a fixing concentration composition part (hereinafter also referred to as a fixing agent part).

  In development processing in minilabs, in addition to the above-mentioned transportation convenience, speeding up of processing for user service and reduction of replenishment for reducing waste liquid discharge are also desired. In order to reduce the replenishment and speed of the bleach-fixing process, it is conceivable to increase the concentration of the bleaching agent and lower the pH in order to maintain the bleaching performance of the bleach-fixing solution. However, when the pH of the fixing agent part is lowered, decomposition and precipitation of the fixing agent occur, so that the fixing agent part cannot be lowered in pH. In addition, when the pH of the bleach part is lowered or the concentration of the bleach is increased, precipitation of different components occurs under low or high temperature storage and use conditions. It will cause trouble. In addition, there is a problem that the stability over time is lowered at a high temperature, and the bleaching performance is lowered due to decomposition of the bleaching agent into a ferrous compound. As described above, the high concentration and low pH of the bleaching agent part have a problem of impairing the storage stability and handling of the processing agent.

  The requirements for the bleaching concentrate composition are such that the components such as the bleaching agent do not precipitate even in a dense composition, and the iron (III) complex is reduced and does not change to a ferrous complex, It has characteristics such as bleaching fog resistance that does not cause bleaching fog while having a sufficient bleaching activity, no generation of acetic acid odor that impairs the working environment, and effective silver recovery. However, as described in the above example, where high concentration and low pH impair the storage stability and handling of the treatment agent, bleaching that sufficiently satisfies all of these necessary characteristics and has no secondary defects. A concentrated composition is not obtained.

Conventionally, many technical developments have been made to establish each necessary characteristic of the bleaching concentrate composition. However, when some of the necessary characteristics of the bleaching composition are improved, other necessary characteristics are not satisfied. Along with this, the technology that can establish all necessary characteristics has not yet been presented.
For example, Patent Document 1 discloses that 1,3-propanediaminetetraacetic acid iron (III) complex can be used to speed up processing and improve desilvering properties, but this technique increases bleaching fog. Therefore, it is unsuitable for color paper processing. Patent Document 2 discloses that precipitation precipitation in a bleach-fixing processing tank or the like can be prevented by using a diethylenetriaminepentaacetic acid iron (III) complex. However, this technique removes yellow edge stains during color paper processing. It has a defect that occurs. Further, Patent Document 3 discloses that the odor of the working environment can be improved by using a polybasic organic acid, but this technique suppresses the swelling of the emulsion layer of the light-sensitive material to be processed, thereby reducing the bleaching speed. Will be reduced. Patent Document 4 discloses that an organic acid iron (III) complex having an oxidation-reduction potential of 200 mV or more and an organic acid having a specific pKa are used to speed up bleaching and improve desilvering properties. This technique reduces silver recovery efficiency from bleach-fixer overflow.

  In contrast to these prior arts, Patent Document 5 discloses that the aminopolycarboxylate iron (III) complex is increased in concentration to 0.5 mol / L or more, and the pH is set low as 2.0 to 3.5. In addition, the presence of an aminopolycarboxylic acid that is not complex-bonded reduces the precipitation over time, ensures stability that the iron (III) complex is reduced and does not change to a ferrous complex, and has an acetic acid odor. This has led to the discovery of a bleaching concentrate composition that is excellent in rapid processing suitability and low replenishment.

However, even with this improved bleach-concentrated composition, precipitation of iron occurs even during long-term storage (especially when the storage temperature is high), and in the state of a bleach-fixing solution prepared by mixing with a fixing agent, a small amount of processing is required. Instability with time such as formation of sulfide precipitates (especially when diluted in a washing tank in the post-bath of the bleach-fixing solution) is a disadvantage. Furthermore, the resistance to bleaching fog is insufficient. In order to solve this problem, reducing the amount of the bleaching agent was not considered at all because it was thought that the desilvering property would be lowered.
As can be seen from the above prior art, no means has yet been found to satisfy all of the required properties required for bleach concentrate compositions.

The above-mentioned prior art relating to the invention of this application includes the following documents.
JP-A-2-103040 Japanese Patent Laid-Open No. 61-118752 Japanese Patent Laid-Open No. 3-155548 Japanese Patent Laid-Open No. 5-72694 JP 2004-53921 A

The present invention has been made from the above-mentioned background, and its purpose is stability over time as a bleaching concentrated composition (precipitation precipitation resistance) and stability during use of the prepared bleach-fixing solution (sulfurization resistance), It is an object of the present invention to provide a bleach-fixing concentration treatment composition which is resistant to bleaching fog, eliminates acetic acid odor, and ensures silver recovery efficiency.
The second object of the present invention is to provide a bleach-fixing processing method that is good even when the photographic quality relating to bleaching is rapidly processed using a bleach-fixing solution obtained by combining the above-described bleaching-concentrating composition with the fixing-concentrating composition. It is in.

The present inventor found that, among the components of the bleaching part, both uncomplexed ethylenediaminetetraacetic acid (hereinafter also referred to as free ethylenediaminetetraacetic acid) and ethylenediaminetetraacetic acid iron (III) complex salt exist in a stable dissolved state. As a result of diligent examination of various salt concentrations, pH, and buffering agent concentrations, the ethylenediaminetetraacetic acid iron (III) complex salt concentration was reduced to a specific salt concentration of 0.5 mol / L or less. By adding acetic acid to a specific concentration of iron (III) complex salt of ethylenediaminetetraacetate, the above-described low temperature precipitation, high temperature precipitation, and deterioration of stability over time at high temperature can be prevented without impairing desilvering properties. It can be newly found that there is a concentration range of pH and a specific buffer (a specific pKa dibasic acid), and the present invention has been reached based on this discovery. Furthermore, the reduction of the iron salt concentration in the bleach-fixing solution improved the resistance to sulfurization and the resistance to bleaching fog, and the silver recovery efficiency could be remarkably improved.
That is, the above object is achieved by the present invention having the following configuration.

1. A bleaching concentrated composition comprising a single liquid satisfying the following compositional requirements (A) to (D).
(A) 0.10 to 0.42 mol / liter of ethylenediaminetetraacetic acid iron (III) complex salt as a bleaching agent,
(B) containing 0.5 to 30 mol% of uncomplexed ethylenediaminetetraacetic acid with respect to the bleaching agent,
(C) It contains 0.10 to 0.40 mol / liter of dibasic acid having a pKa of 2.0 to 5.0, and (D) pH is 2.0 to 3.5.
2. 2. The bleaching concentrated composition as described in 1 above, which does not contain an azole compound.

3. 3. The bleaching concentrated composition as described in 1 or 2 above, wherein the bleaching concentrated composition is diluted with water 1.2 to 5.0 times.
4). The bleaching concentrated composition according to any one of the above 1 to 3 and a fixing concentrated composition containing 1.0 to 3.0 mol / liter of thiosulfate were each diluted with water 1.2 to 5.0 times. A silver halide color photographic light-sensitive material characterized in that a bleaching / fixing tank is replenished at a ratio of 1: 1 and the immersion time of the silver halide photographic light-sensitive material in the bleach-fixing tank solution is 10 to 30 seconds. Processing method.

The gist of the present invention is that a dibasic acid having a pKa of 2.0 to 5.0 is first contained in an amount of 0.10 to 0.40 mol / liter, thereby eliminating the acetic acid odor. Further, precipitation resistance that cannot be obtained even when other conventional general-purpose acids are used and low pH is set, and thus stability over time is obtained. The second essential point of the present invention is that, based on this dibasic acid and its concentration conditions, an ethylenediaminetetraacetic acid iron (III) complex salt is further selected as a bleaching agent, and the ethylenediaminetetraacetic acid iron (III) complex salt concentration is reduced to 0. Using a specific salt concentration of 5 mol / L or less and adding a specific concentration of free ethylenediaminetetraacetic acid to the iron (III) complex salt of ethylenediaminetetraacetate, low temperature precipitation without impairing the desilvering property, In addition, the deterioration of stability over time at high temperatures has been improved.
The above-mentioned components used in the bleaching concentrated composition of the present invention are components of a conventionally known bleaching agent composition, but the above-mentioned component composition region (dibasic acid having a specific pKa, its concentration condition, iron ethylenediaminetetraacetate ( (III) Complex salt, free ethylenediaminetetraacetic acid, pH range of 3.5 or lower and 2.0 or higher) newly found that there is a region where the bleaching concentrated composition is stable and the bleaching performance is maintained well. In addition, the existence of such a special composition region is not conceivable.

A further feature of the present invention is that the bleaching composition having the above composition has rapid bleach-fixability despite the use of an ethylenediaminetetraacetic acid iron (III) complex salt having a low oxidation potential as a bleaching agent. Therefore, by setting the bleaching agent composition in the above specific region, the finish quality is maintained, and the low replenishment treatment of ²⁰ to 50 ml / m ² without causing precipitation or deterioration of the treatment liquid and the like. It is possible to perform rapid and low replenishment processing such as short-time bleach-fixing processing of 30 seconds or less.

  The bleaching concentrated composition for a silver halide photographic light-sensitive material of the present invention composed of a specific concentration range of a specific component compound and a specific pH range is composed of one part and is stable over time (precipitation resistance). And bleach-fixing composition prepared together with the fixing composition, a bleach-concentrated composition with stability (sulfuration resistance), bleaching fog resistance, elimination of acetic acid odor, and silver recovery efficiency. Sex is also maintained.

The present invention is described in further detail below.
The bleach-fixing solution concentration treatment composition is preferably composed of a bleaching agent part and a fixing agent part. The present invention is an invention relating to the bleach part or bleach concentrate composition therein. The invention also relates to a bleach-fixing replenishing method using the same.
In the present invention, the bleaching agent part and the fixing agent part may be mixed and diluted in advance to prepare and use as a bleach-fixing replenisher, or the bleaching agent part and the fixing agent part may be directly replenished directly to the bleach-fixing tank, respectively. In this case, it may be allowed to function substantially as a bleach-fixing replenisher in the tank, but the latter mode of replenishing the tank separately is preferable from the viewpoint of simplification of the processing operation because the purpose of the invention is more remarkably exhibited. .

The bleach-concentrating composition of the present invention comprises a bleach-fixing solution for a silver halide color photographic light-sensitive material comprising a bleach-concentrating composition part containing a bleaching agent and a fixing-concentrating composition part containing a fixing agent. It is a constituent part of the concentrated composition and is characterized by comprising a single liquid that satisfies the following compositional requirements (A) to (D).
(A) 0.10 to 0.42 mol / liter of ethylenediaminetetraacetic acid iron (III) complex salt as a bleaching agent,
(B) containing 0.5 to 10 mol% of uncomplexed ethylenediaminetetraacetic acid with respect to the bleaching agent,
(C) A dibasic acid having a pKa of 2.0 to 5.0 is contained in an amount of 0.10 to 0.40 mol / liter, and (D) the pH is 2.0 to 3.5.

In the present invention, ethylenediaminetetraacetic acid iron (III) complex salt is used as a bleaching agent, and the concentration in the concentrated composition is 0.10 to 0.42 mol / liter. A preferred concentration range is 0.15 to 0.0.40 mol / liter, more preferably 0.20 to 0.35 mol / liter.
When the composition has a high concentration exceeding the above-mentioned concentration range, precipitates are likely to be formed over time, and when the concentration is lower than the lower limit of the above-mentioned concentration range, a rapid bleach-fixing speed cannot be obtained and a desilvering defect tends to occur.

The bleaching concentrated composition contains free ethylenediaminetetraacetic acid in an amount of 0.5 to 30 mol%, preferably 2.0 to 20 mol%, more preferably 3 to the ethylenediaminetetraacetic acid iron (III) complex salt. 0.0 to 15 mol% is contained.
If the concentration ratio of uncomplexed (free) ethylenediaminetetraacetic acid to iron (III) complex salt exceeds 30 mol%, precipitation of free acid is likely to occur, and the stabilizing effect on iron (III) complex salt is further increased. Less. On the other hand, if the concentration of the free acid is less than 0.5 mol%, iron precipitates will occur at high temperatures.

The pH of the bleaching concentrated composition is 2.0 to 3.5, preferably 2.2 to 3.3, and more preferably 2.4 to 3.0.
A dibasic acid having a pKa of 2.0 to 5.0 is contained in an amount of 0.10 to 0.40 mol / liter. The preferred content is 0.15 to 0.35 mol / liter, more preferably 0.20 to 0.30 mol / liter. Dibasic acid with a pKa of 2.0-5.0 inhibits precipitation and changes to iron (II) complexes and hydroxylated complexes in a system in which free ethylenediaminetetraacetic acid and its iron (III) complex salt coexist. The action is a phenomenon seen in the above concentration range and pH range. Moreover, by using in the said density | concentration range, the pH in a bleach-fixing tank liquid can be stabilized in a preferable range, and sulfuration resistance, bleaching fog resistance, and silver collection | recovery efficiency improve, respectively.

  The bleaching concentrated composition of the present invention is preferably diluted with water before use. The dilution ratio is 1.2 to 5.0 (volume ratio standard), preferably 1.3 to 3.0. This dilution means that a concentration range suitable for storage stability and transportability is adjusted to a concentration condition convenient for use as a bleach-fixing replenisher. Needless to say, the water used for dilution may be an overflow liquid or an overflow liquid of a rinse tank.

  As a mode for replenishing the bleach-fixing tank, it is preferable that the fixing concentrated composition is diluted with water to the same extent and added to the bleach-fixing tank at a replenishment rate corresponding to the processing speed of the photosensitive material to be processed. is there. However, it is also possible to use an embodiment in which the bleaching concentration composition and the fixing concentration composition are directly replenished to the bleach-fixing tank without diluting with water, and at the same time, the overflow liquid of the water or the rinsing tank is replenished. Further, as described above, the bleaching concentration composition, the fixing concentration composition, and the overflow solution of water or a rinsing tank or a color developing tank are mixed to prepare a bleach-fixing replenisher, and this is directly replenished to the bleach-fixing tank. I can take it.

  Particularly preferably, the bleaching concentrated composition of the present invention and the fixing concentrated composition containing 1.0 to 3.0 mol / liter of thiosulfate were each diluted with water 1.2 to 5.0 times. In this processing method, the bleach-fixing tank is replenished at a ratio of 1: 1, and the immersion time of the silver halide photographic light-sensitive material in the bleach-fixing tank solution is 10 to 30 seconds. That is, in this embodiment, rapid processing is possible even if the bleaching agent is a relatively low oxidation potential compound such as an iron (III) complex of ethylenediaminetetraacetate.

  In many cases, the bleaching concentrate composition and the bleach-fixing replenisher include imidazoles such as imidazole and dimethylimidazole, pyrimidine derivatives, triazoles, thiadiazoles, oxaniazoles, for the purpose of accelerating bleaching or reducing bleaching fog. An azole compound such as 2-picolinic acid is included. However, when an azole compound is added to the bleaching concentrated composition of the present invention, precipitates are generated during storage of the concentrated solution at a low temperature, and the bleaching rate is reduced, so that the effects of the present invention are hardly obtained. Become. Therefore, it is preferable that an azole compound is not included substantially.

  In the bleaching concentrated composition of the present invention, other known bleaching agents can be used as a bleaching agent in addition to the iron (III) complex salt of ethylenediaminetetraacetate. Bleaching agents that can be used in combination include iron (III) complex salts of aminopolyacetates other than iron (III) complex salts of ethylenediaminetetraacetate, iron (III) complex salts of organic acids such as citric acid, tartaric acid, malic acid, persulfates, hydrogen peroxide Etc. However, when these second bleaching agents are used in combination, the content thereof is 50 mol% or less, preferably 30 mol% or less, and more preferably not contained (that is, irondiamine (III) complex salt of ethylenediamine tetraacetate (ie Ethylenediaminetetraacetic acid iron (III) complex salt only).

  Bleach fixer replenisher mixed with bleach part and fixer part, diluted with water, composition equivalent to bleach fixer replenishment combined with bleach part, fixer part and color developer tank overflow, or bleach fixer tank solution The bleaching agent concentration is 0.01 to 1.0 mol / L, preferably 0.03 to 0.80 mol / L, more preferably 0.05 to 0.70 mol / L, still more preferably 0.07. It is determined to be ˜0.50 mol / L.

The bleach part contains 0.10 to 0.40 mol / liter of dibasic acid having a pKa of 2.0 to 5.0. If the pKa of the dibasic acid is less than 2.0, free acid precipitation is likely to occur, and conversely if the pKa exceeds 5.0, hydrolysis precipitation of the iron (III) complex bleaching agent is likely to occur. A preferable dibasic acid has a pKa of 3.5 to 4.5.
On the other hand, even if the content of the dibasic acid is further increased from the range of 0.10 to 0.40 mol / liter, further composition stabilizing effect is poor, and insolubility of the composition is likely to occur. The effect of the invention cannot be obtained on the low concentration side from the range.
The bleaching agent part may contain other monobasic acid or polybasic acid as long as the dibasic acid is contained in an amount of 0.10 to 0.40 mol / liter, but is preferably not contained.

Specific examples of the dibasic acid having a pKa of 2.0 to 5.0 include oxalic acid, maleic acid, malonic acid, glutaric acid, phthalic acid, isophthalic acid, adipic acid, and the like. Excellent in that there is no bleaching delay.
Preferred dibasic acids are succinic acid, maleic acid, malonic acid and glutaric acid, with succinic acid being most preferred.

  The fixing agent part constituting the bleach-fixing solution processing composition in combination with the bleaching agent part is a known fixing chemical, that is, a thiosulfate such as sodium thiosulfate or ammonium thiosulfate, sodium thiocyanate, ammonium thiocyanate, etc. 1 or 2 selected from water-soluble silver halide solubilizers such as thioether compounds such as thiocyanate, ethylenebisthioglycolic acid, 3,6-dithia-1,8-octanediol, and thioureas The above can be mixed and contained. A special bleach-fixing solution comprising a combination of a fixing agent described in JP-A-55-155354 and a large amount of a halide such as potassium iodide can also be used. In the present invention, it is preferable to use thiosulfate, particularly ammonium thiosulfate. The concentration of the fixing chemical in the fixing agent part is determined by the bleach-fixing replenisher prepared from the bleaching agent part and the fixing agent part. It is preferably designed to be 0.3 to 3 mol per liter of the corresponding liquid, more preferably 0.5 to 2.0 mol.

  Fixer parts include preservatives such as sulfites (eg, sodium sulfite, potassium sulfite, ammonium sulfite, etc.), bisulfites (eg, ammonium bisulfite, sodium bisulfite, potassium bisulfite, etc.), Sulphite ion releasing compounds such as sulfites (for example, potassium metabisulfite, sodium metabisulfite, ammonium metabisulfite, etc.), arylsulfinic acids such as p-toluenesulfinic acid, m-carboxybenzenesulfinic acid, etc. It is preferable to contain. These compounds are preferably contained in an amount of about 0.02 to 1.0 mol / L (as the concentration of the prepared treatment liquid) in terms of sulfite ions or sulfinate ions.

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

  The following describes the bleach-fix solution prepared by mixing the bleach part and the fixer part, and adding a little water if necessary, but it can be contained in either the bleach part or the fixer part. A good bleach-fixing solution component is also described in this section.

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

  In addition, one or both of the bleaching agent part and the fixing agent part of the bleach-fixing treatment composition may contain various other fluorescent brighteners, antifoaming agents, surfactants, polyvinylpyrrolidone, and the like. .

  In general, the bleach-fixing solution processing composition is supplied in a form housed in a container. The container for the bleach-containing treatment composition part preferably has a certain oxygen transmission rate in view of the stability of the composition over time, and is different from other treatment agent containers in this respect. In order to ensure oxygen permeability, it is not always necessary to select an oxygen permeable container material. For example, the airtightness may be relaxed by the structure of the container mouth. The oxygen permeability is preferably 4 mL or more per day, but is preferably 13 mL or less from the limitation of the wall thickness for maintaining the shape of the container.

Examples of preferred containers used for typical storage configurations of bleach are high density polyethylene (hereinafter referred to as HDPE) having a density of 0.941 to 0.969 and a melt index in the range of 0.3 to 5.0 g / 10 min. Is a container made as a single component resin. A more preferable density is 0.951 to 0.969, and still more preferably 0.955 to 0.965. Moreover, a more preferable melt index is 0.3-5.0, More preferably, it is 0.3-4.0. The melt index is a value measured under a load of 2.16 kg at a temperature of 190 ° C. according to the method defined in ASTM D1238. The container is preferably 500-1500 μm thick. However, the processing agent container used in the present invention is not limited to the HDPE container that is convenient for mounting on a developing machine, and other HDPE such as polyethylene terephthalate (PET), polyvinyl chloride (PVC), and low density polyethylene (LDPE). Other than conventional container materials, and even HDPE, containers made from materials other than the above ranges of density and melt index can be used.
In addition, a form accommodated in a so-called cubitener inserted into a reinforcing cardboard in accordance with its inner method is also preferable.
Although the container mentioned later can also be used as other processing agent containers, it is desirable that the oxygen permeation rate is ensured.

Next, a color processing step using the bleaching concentrated composition of the present invention will be described.
The color development processing to which the bleaching concentrated composition of the present invention is applied consists of a color development step, a desilvering step, a water washing or stabilizing bath step and a drying step, and a rinsing step, an intermediate water washing step, a neutralization step between each step. It is also possible to insert auxiliary processes such as The desilvering step is performed by a one-step process using a bleach-fixing solution, and the bleaching concentrated composition is used in this step. In addition to a water washing alternative stabilizing bath instead of the water washing step, an image stabilizing bath for the purpose of image stabilization can be provided between the water washing or stabilizing bath step and the drying step.

Depending on the composition of the bleach-fixing solution processing composition of the present invention, the replenishing amount of the bleach-fixing solution can be remarkably reduced, and is preferably ^{20 to} 50 ml, more preferably 25 to 45 ml per 1 m ² of the photosensitive material. Most preferably, it is 25 to 40 ml. The replenishment amount of the bleach-fixing solution is preferably divided into a bleaching agent part and a fixing agent part. In this case, the replenishment amount of the bleach-fixing solution indicates the total replenishment amount of the bleaching agent part and the fixing agent part. is there. Moreover, it is preferable that the replenishment amount of the rinsing liquid (washing water and / or stabilizing liquid) is 50 ml to 200 ml as a whole.

  Here, the color development time (that is, the time for performing the color development process) is preferably 100 seconds or less, more preferably 60 seconds or less, and further preferably 40 seconds or less and 6 seconds or more. Similarly, the bleach-fixing time (that is, the time for performing the bleach-fixing step) is preferably 150 seconds or shorter, more preferably 90 seconds or shorter, and even more preferably 45 seconds or shorter and 6 seconds or longer. Further, the rinsing (washing or stabilizing) time (that is, the time for performing the rinsing step) is preferably 90 seconds or less, more preferably 60 seconds or less, and further preferably 30 seconds or less and 10 seconds or more.

  The color development time refers to the time from when the photosensitive material enters the color developer until it enters the bleach-fixing solution in the next processing step. When processed with an automatic processor, the photosensitive material is immersed in the color developer (so-called submerged time), and the photosensitive material leaves the color developer and becomes a bleach-fixing solution in the next processing step. The sum of both the time during which the air is conveyed toward the air (so-called air time) is the color development time. Similarly, the bleach-fixing time refers to the time from when the photosensitive material enters the bleach-fixing solution until the next washing or stabilizing bath. The rinsing (washing or stabilization) time refers to the time from when the photosensitive material enters the rinsing solution (washing or stabilization solution) to the drying step.

  The processing solution temperature in the color development process, the bleach-fixing process, and the rinsing process is generally 30 to 40 ° C., but it is also possible to perform high temperature rapid processing at 38 to 60 ° C., more preferably 40 to 50 ° C. It is an aspect.

The amount of rinsing solution can be set in a wide range depending on the characteristics of the photosensitive material (for example, depending on the material used such as coupler) and application, the temperature of the rinsing solution (washing water), the number of rinsing solutions (washing tank) (stage number), and various other conditions. Can do. Among these, the relationship between the number of rinse liquid tanks (water washing tanks) and the amount of water in the multi-stage countercurrent system is the Journal of the Society of Motion Picture and Motion of Picture Picture and Television Engineers) Vol. 64, p. It can be determined by the method described in 248-253 (May 1955).
Usually, the number of stages in the multistage countercurrent system is preferably from 3 to 10, particularly from 3 to 5.

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

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

The components of other processing compositions used in the color development process together with the above-described bleach-fixing solution processing composition and processing solutions prepared from them will be described.
The processing composition, including the above-described bleach-fixing solution processing composition, is mixed with a solvent such as water at a ratio determined upon use to prepare a mother liquid (tank liquid) or a replenisher. In the book, unless there is a special meaning to distinguish between the tank liquid and the replenisher liquid, both are expressed as a working liquid.

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

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

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

  An organic preservative may be added to the color developer as a preservative. The organic preservative refers to all organic compounds that reduce the deterioration rate of the aromatic primary amine color developing agent by being contained in the processing solution of the photosensitive material. That is, it is an organic compound having a function of preventing air oxidation of a color developing agent, among others, hydroxylamine derivatives, 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 are particularly effective organic preservatives. These are disclosed in JP-A 63-4235, 63-30845, 63-21647, 63-44655, 63-53551, 63-43140, 63-56654, 63- 58346, 63-43138, 63-146041, 63-44657, 63-44656, U.S. Pat.Nos. 3,615,503, 2,494,903, JP 52-143020, JP 48-30496 It is disclosed in each gazette or specification such as No ..

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

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

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

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

  It is preferable to add the developer so that the pH of the developer is 9.0 to 13.5 and the pH of the replenisher is 9.0 to 13.5. As possible, an alkali agent, a buffering agent and, if necessary, an acid agent can be included.

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

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

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

  If necessary, an optional development accelerator can be added to the color developer according to the present invention. Examples of the development accelerator include thioether compounds described in JP-B-37-16088, p-phenylenediamine compounds described in JP-A-52-49829, JP-A-50-137726, and the like. A quaternary ammonium salt described in U.S. Pat. No. 2,494,903, an amine compound, a polyalkylene oxide described in JP-B-42-25201, and other 1-phenyl-3-pyrazolidones or imidazoles. It can be added as necessary. The added amount in the composition is determined so that the concentration thereof is 0.001 to 0.2 mol, preferably 0.01 to 0.05 mol, per liter for both the developer and replenisher prepared from the processing agent. .

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

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

  After completion of fixing or bleach-fixing, a water-washing alternative stabilizing bath or a stabilizing bath for image stabilization is often used, but these baths are low in concentration and the utility of the processing agent is not great, but it is necessary. A treating agent can be produced. As the stabilizing bath treatment agent, the method of reducing calcium and magnesium described in JP-A-62-288838 can be used very effectively. Further, chlorinated fungicides such as isothiazolone compounds and siabendazoles described in JP-A-57-8542, chlorinated sodium isocyanurate described in JP-A-61-120145, JP-A-61-267761 Benzotriazole, copper ion, and other publications described in the gazette, Hiroshi Horiguchi, “Chemistry of Antibacterial and Antifungal” (1986) Sankyo Publishing, Hygiene Technology Association, “Microbial Decontamination, Sterilization, Antifungal Technology” (1982) The bactericides described in the “Industrial Antibacterial and Antifungal Encyclopedia” (1986) edited by the Industrial Technology Association of Japan and the Japanese Society for Antibacterial and Antifungal Society may also be used.

The development processing method according to the present invention is performed using an automatic developing machine. The automatic processor preferably used in the present invention will be described below.
In the present invention, it is preferable that the linear speed of conveyance of the automatic processor is 100 mm / second or less. It is more preferably 27.8 mm / second to 80 mm / second, particularly preferably 27.8 mm / second to 50 mm / second.

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

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

Various component materials are used in the automatic processor, and preferable materials are described below.
The tank material such as the treatment tank and the temperature control tank is preferably modified PPO (modified polyphenylene oxide) or modified PPE (modified polyphenylene ether) resin. Examples of the modified PPO include “Noryl” manufactured by GE Plastics Japan, and the modified PPE includes “Zylon” manufactured by Asahi Kasei Kogyo, “Iupiace” manufactured by Mitsubishi Gas Chemical, and the like. Moreover, these materials are suitable for parts that may come into contact with the processing liquid such as processing racks and crossovers.

Resin such as PVC (polyvinyl chloride), PP (polypropylene), PE (polyethylene), TPX (polymethylpentene) is suitable for the roller material of the processing section. These materials can also be used for other processing liquid contact portions. In addition, PE resin is preferable also for the material of the replenishment tank by blow formation.
Materials for processing parts, gears, sprockets, bearings, etc. include PA (polyamide), PBT (polybutylene terephthalate), UHMPE (ultra high molecular weight polyethylene), PPS (polyphenylene sulfide), LCP (fully aromatic polyester resin, liquid crystal polymer) ) Etc. are suitable.
PA resin is polyamide resin such as 66 nylon, 12 nylon, and 6 nylon, and those containing glass fiber or carbon fiber are strong against swelling by the treatment liquid and can be used.

High molecular weight products such as MC nylon and compression molded products can be used without fiber reinforcement. UHMPE resin is suitable for unreinforced products such as “Lubema” manufactured by Mitsui Petrochemical Co., Ltd., “Hi-X Million” Sakushin Kogyo Co., Ltd. “New Light”, Asahi Kasei Kogyo Co., Ltd. “Sun Fine”, etc. Are suitable. The molecular weight is preferably 1,000,000 or more, more preferably 1,000,000 to 5,000,000.
The PPS resin is preferably glass fiber or carbon fiber reinforced. The LCP resin includes ICI Japan Co., Ltd. “Victrex”, Sumitomo Chemical Co., Ltd. “Econol”, Nippon Oil Co., Ltd. “Zyder”, Polyplastics Co., Ltd. “Vectra”.
In particular, the material of the conveyor belt is preferably ultrahigh strength polyethylene fiber or polyvinylidene fluoride resin described in Japanese Patent Application No. 2-276886.
As a soft material such as a squeeze roller, a foamed vinyl chloride resin, a foamed silicon resin, and a foamed urethane resin are suitable. Examples of the urethane foam resin include “Rubicel” manufactured by Toyo Polymer Co., Ltd.
EPDM rubber, silicon rubber, Viton rubber and the like are preferable as rubber materials such as a pipe joint, an agitation jet pipe joint, and a sealing material.

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

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

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

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

Conventional containers for processing liquids include single layer materials such as high density polyethylene (HDPE), polyvinyl chloride resin (PVC), polyethylene terephthalate (PET), and multilayer materials such as nylon / polyethylene (NY / PE). The rigid container used can be used.
Further, after the contents are discharged and emptied, it is possible to use a liquid container having a flexibility that can easily reduce the volume of the container, that is, reduce the required space. As an example, it is preferable to use a container having the above flexibility. A specific example of the flexible container is a liquid container in which a hard mouth protruding upward from a flexible container body is opened and closed by a lid member engaged therewith, the container body and the mouth And a container having a bellows portion in at least a part in the height direction of the container body (FIGS. 1 and 2 described in JP-A-7-5670).

[Applicable photosensitive material]
Next, a silver halide color photographic light-sensitive material to which the color developer replenisher composition of the present invention is applied (hereinafter sometimes simply referred to as “photosensitive material”) will be described.
The light-sensitive material used in the present invention is a color photographic light-sensitive material for photographing and color printing paper for color printing, which are widely used in the photographic market as described above in relation to the object and background of the invention. At least one photosensitive layer is provided on the support. A typical example is a silver halide photographic light-sensitive material having at least one photosensitive layer comprising a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivity on a support. It is.

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

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

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

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

  Next, the photosensitive silver halide used in the present invention will be described. The silver halide of the present invention is substantially a cubic or tetradecahedral crystal grain having a {100} face (these grains may have rounded vertices and may have higher order faces), 8 It is preferable that the crystal lattice of the plane body and the main plane are composed of tabular grains having an aspect ratio of 2 or more and comprising {100} planes or {111} planes. The aspect ratio is a value obtained by dividing the diameter of a circle corresponding to the projected area by the thickness of the particle. For tabular grains having a main surface of {100} face or {111} face, reference can be made to columns 33 (P7) to P840 (P8) of JP-A No. 2000-352794. In the present invention, a cube is most preferable. The particle size is preferably 0.5 μm or less, more preferably 0.4 μm or less, in terms of cubic conversion side length.

  In this specification, the cube side length is represented by the length of one side when a volume equal to the volume of each particle is converted into a cube, and in this specification, the cube side length also indicates the same meaning. The emulsion of the present invention is preferably composed of grains having a monodispersed grain size distribution. The variation system number of the cubic conversion side length of all the particles of the present invention is preferably 20% or less, more preferably 15% or less, and still more preferably 10% or less. The coefficient of variation of the cubic conversion side length is expressed as a percentage of the average side length of the standard deviation of one side of the cubic conversion side length of each particle. At this time, for the purpose of obtaining a wide latitude, it is preferable to use the above monodispersed emulsion by blending it in the same layer or to carry out multilayer coating.

  The silver halide emulsion used in the present invention may contain silver halide grains other than the silver halide grains (that is, specific silver halide grains) contained in the silver halide emulsion defined in the present invention. However, the silver halide emulsion defined in the present invention requires that 50% or more of the total projected area of all grains be silver halide grains as defined in the present invention, and preferably 80% or more. More preferably, it is 90% or more.

  As the silver halide emulsion used in the present invention, an emulsion containing silver halide grains having a specific silver halide content is used, and the silver chloride content is 90 mol% or more from the viewpoint of rapid processability. The silver chloride content is preferably 93 mol% or more, more preferably 95 mol% or more. The silver bromide content is preferably 0.1 to 7 mol%, more preferably 0.5 to 5 mol%, since it is a high contrast and has excellent latent image stability. The silver iodide content is preferably 0.02-1 mol%, more preferably 0.05-0.50 mol%, and more preferably 0.07-0. 40 mol% is most preferred. The silver halide grains of the present invention are preferably silver iodobromochloride grains, and more preferably silver iodobromochloride grains having the above halogen composition.

  The silver halide grains in the silver halide emulsion used in the present invention preferably have a silver bromide-containing phase and / or a silver iodide-containing phase. Here, the silver bromide or silver iodide-containing phase means a portion where the concentration of silver bromide or silver iodide is higher than the surroundings. The halogen composition of the silver bromide-containing phase or silver iodide-containing phase and its surroundings may change continuously or may change sharply. Such a silver bromide or silver iodide-containing phase may form a layer having a substantially constant width at a certain portion in the grain, or may be a maximum point having no spread. The local silver bromide content of the silver bromide-containing phase is preferably 2 mol% or more, more preferably 3 to 50 mol%, and most preferably 4 to 20 mol%. The local silver iodide content of the silver iodide-containing phase is preferably 0.3 mol% or more, more preferably 0.5 to 8 mol%, and more preferably 1 to 5 mol%. Most preferred. Further, a plurality of such silver bromide or silver iodide-containing phases may be formed in layers in each grain, and the silver bromide or silver iodide content may be different, but at least one of each. It is necessary to have a contained phase of

  It is important that the silver bromide-containing phase or the silver iodide-containing phase of the silver halide emulsion used in the present invention is layered so as to surround each grain. In one preferred embodiment, the silver bromide-containing phase or the silver iodide-containing phase formed in layers so as to surround the grains has a uniform concentration distribution in the circumferential direction of the grains in each phase. However, in the silver bromide-containing phase or silver iodide-containing phase that are layered so as to surround the grain, the maximum or minimum point of the silver bromide or silver iodide concentration exists in the circumferential direction of the grain, and the concentration distribution You may have. For example, when a silver bromide-containing phase or silver iodide-containing phase is formed in a layer so as to surround the grain in the vicinity of the grain surface, the silver bromide or silver iodide concentration at the grain corner or edge is different from the main surface. There is a case. In addition to the silver bromide-containing phase and the silver iodide-containing phase that are layered so as to surround the grain, the silver bromide-containing phase that is completely isolated in a specific part of the surface of the grain and does not surround the grain Alternatively, there may be a silver iodide containing phase.

  When the silver halide emulsion used in the present invention contains a silver bromide-containing phase, the silver bromide-containing phase is preferably formed in a layered manner so as to have a silver bromide concentration maximum inside the grain. Further, when the silver halide emulsion of the present invention contains a silver iodide-containing phase, the silver iodide-containing phase is preferably formed in a layered manner so as to have a silver iodide concentration maximum on the surface of the grain. Such a silver bromide-containing phase or silver iodide-containing phase is composed of a silver amount of 3% to 30% of the grain volume in order to increase the local concentration with a smaller silver bromide or silver iodide content. It is preferable that the silver content is 3% or more and 15% or less.

  The silver halide emulsion used in the present invention preferably contains both a silver bromide-containing phase and a silver iodide-containing phase. In this case, the silver bromide-containing phase and the silver iodide-containing phase may be at the same place or different places in the grain, but it is preferable that the silver bromide-containing phase and the silver iodide-containing phase are in different places from the viewpoint of facilitating control of grain formation. Further, the silver bromide-containing phase may contain silver iodide, and conversely, the silver iodide-containing phase may contain silver bromide. In general, iodide added during the formation of high silver chloride grains tends to ooze out on the grain surface than bromide, so the silver iodide-containing phase tends to be formed near the grain surface. Therefore, when the silver bromide-containing phase and the silver iodide-containing phase are at different locations in the grain, the silver bromide-containing phase is preferably formed inside the silver iodide-containing phase. In such a case, another silver bromide-containing phase may be provided further outside the silver iodide-containing phase near the grain surface.

  The silver bromide content or silver iodide content necessary for exhibiting the effects of the present invention such as high sensitivity and high contrast is such that the silver bromide-containing phase or silver iodide-containing phase is formed inside the grain. There is a risk that the amount of silver chloride may be reduced more than necessary, and the rapid processability may be impaired. Therefore, in order to concentrate these functions for controlling the photographic action near the surface in the grain, the silver bromide-containing phase and the silver iodide-containing phase are preferably adjacent to each other. From these points, the silver bromide-containing phase is formed at any of the positions of 50% to 100% of the grain volume as measured from the inside, and the silver iodide-containing phase is any of the positions at 85% to 100% of the grain volume. It is preferable to form it. Further, the silver bromide-containing phase is formed at any position from 70% to 95% of the grain volume, and the silver iodide-containing phase is further formed at any position from 90% to 100% of the grain volume. preferable.

  In order to incorporate silver bromide or silver iodide into a silver halide emulsion, bromide or iodide ions can be introduced by adding a bromide salt or an iodide salt solution alone, or by adding a silver salt solution and a high chloride salt. Along with the addition of the solution, a bromide salt or iodide salt solution may be added. In the latter case, bromide salt or iodide salt solution and high chloride salt solution may be added separately or as a mixed solution of bromide salt or iodide salt and high chloride salt. The bromide salt or iodide salt is added in the form of a soluble salt such as an alkali or alkaline earth bromide salt or iodide salt. Alternatively, it can be introduced by cleaving bromide ions or iodide ions from organic molecules described in US Pat. No. 5,389,508. As another bromide or iodide ion source, fine silver bromide grains or fine silver iodide grains can also be used.

The addition of the bromide salt or iodide salt solution may be concentrated during a period of grain formation or may be performed over a certain period. The position of introduction of iodide ions into the high chloride emulsion is limited in obtaining a high sensitivity and low fog emulsion. Iodide ions are introduced more into the emulsion grains and the increase in sensitivity is smaller. Therefore, the iodide salt solution is preferably added outside 50% of the grain volume, more preferably outside 70%, and most preferably outside 85%. Further, the addition of the iodide salt solution is preferably completed within 98% of the grain volume, and most preferably within 96%. The addition of the iodide salt solution is completed slightly inside from the grain surface, whereby an emulsion with higher sensitivity and lower covering can be obtained.
On the other hand, the addition of the bromide salt solution is preferably performed outside 50% of the particle volume, more preferably outside 70%.

  Distribution of bromide or iodide ion concentration in the depth direction in the grain is measured by etching / TOF-SIMS (Time of Flight-Secondary Ion Mass Spectrometry) method, for example, using TRIFT II type TOF-SIMS manufactured by Phi Evans. it can. The TOF-SIMS method is specifically described in “Surface Analysis Technology Selection Secondary Ion Mass Spectrometry” Maruzen Co., Ltd. (1999), edited by the Surface Science Society of Japan. When the emulsion grains are analyzed by the etching / TOF-SIMS method, it is possible to analyze that iodide ions ooze out toward the grain surface even when the addition of the iodide salt solution is finished inside the grains. The emulsion of the present invention is analyzed by etching / TOF-SIMS method, and it is preferable that iodide ions have a maximum concentration on the grain surface, and the iodide ion concentration is attenuated toward the inside. It is preferable to have a concentration maximum inside. The local concentration of silver bromide can also be measured by X-ray diffraction if the silver bromide content is somewhat high.

  The silver halide emulsion used in the present invention preferably contains iridium. As the iridium compound, a 6-coordination complex having 6 ligands and having iridium as a central metal is preferable because it can be uniformly incorporated into a silver halide crystal. As one preferred embodiment of the iridium used in the present invention, a hexacoordinate complex having Ir as a central metal having Cl, Br or I as a ligand is preferred, and Ir comprising all six ligands consisting of Cl, Br or I is preferred. A hexacoordinate complex as a central metal is more preferable. In this case, Cl, Br, or I may be mixed in the hexacoordinate complex. It is particularly preferable that a hexacoordinate complex having Ir as a central metal having Cl, Br, or I as a ligand is contained in a silver bromide-containing phase in order to obtain a high gradation at high illumination exposure.

Specific examples of the 6-coordination complex in which all six ligands are composed of Cl, Br or I and having Ir as a central metal are given below, but iridium in the present invention is not limited to these.
[IrCl ₆ ] ^2-
[IrCl ₆ ] ^3-
[IrBr ₆ ] ^2-
[IrBr ₆ ] ^3-
[IrI ₆ ] ^3-

As a different preferred embodiment of iridium used in the present invention, a hexacoordination complex having at least one ligand other than halogen or cyan as a central metal is preferable, and H ₂ O, OH, O, OCN, thiazole or substituted thiazole is preferable. Preferred is a hexacoordination complex having Ir as a central metal and having at least one H ₂ O, OH, O, OCN, thiazole or substituted thiazole as a ligand and the remaining ligands from Cl, Br or I A hexacoordinate complex having Ir as a central metal is more preferable.

Specific examples of 6-coordination complexes having at least one H ₂ O, OH, O, OCN, thiazole or substituted thiazole as a ligand and the remaining ligand consisting of Cl, Br or I as a central metal The iridium in the present invention is not limited to these.

[IrCl ₅ (H ₂ O)] ^2-
[IrCl ₄ (H ₂ O) ₂ ] ^-
[IrCl ₅ (H ₂ O)] ^-
[IrCl ₄ (H ₂ O) ₂ ] ⁰
[IrCl ₅ (OH)] ^3-
[IrCl ₄ (OH) ₂ ] ^2-
[IrCl ₅ (OH)] ^2-
[IrCl ₄ (OH) ₂ ] ^2-
[IrCl ₅ (O)] ^4-
[IrCl ₄ (O) ₂ ] ^5-
[IrCl ₅ (O)] ^3-
[IrCl ₄ (O) ₂ ] ^4-
[IrBr ₅ (H ₂ O)] ^2-
[IrBr ₄ (H ₂ O) ₂ ] ^-
[IrBr ₅ (H ₂ O)] ^-
[IrBr ₄ (H ₂ O) ₂ ] ⁰
[IrBr ₅ (OH)] ^3-
[IrBr ₄ (OH) ₂ ] ^2-
[IrBr ₅ (OH)] ^2-
[IrBr ₄ (OH) ₂ ] ^2-
[IrBr ₅ (O)] ^4-
[IrBr ₄ (O) ₂ ] ^5-
[IrBr ₅ (O)] ^3-
[IrBr ₄ (O) ₂ ] ^4-
[IrCl ₅ (OCN)] ^3-
[IrBr ₅ (OCN)] ^3-
[IrCl ₅ (thiazole)] ^2-
[IrCl ₄ (thiazole) ₂ ] ^-
[IrCl ₃ (thiazole) ₃ ] ⁰
[IrBr ₅ (thiazole)] ^2-
[IrBr ₄ (thiazole) ₂ ] ^-
[IrBr ₃ (thiazole) ₃ ] ⁰
[IrCl ₅ (5-methylthiazole)] ^2-
[IrCl ₄ (5-methylthiazole) ₂ ] ^-
[IrBr ₅ (5-methylthiazole)] ^2-
[IrBr ₄ (5-methylthiazole) ₂ ] ^-
[IrCl ₅ (5-chlorothiazole)] ^2-
[IrCl ₄ (5-chlorothiazole) ₂ ] ^-
[IrBr ₅ (5-chlorothiazole)] ^2-
[IrBr ₄ (5-chlorothiazole) ₂ ] ^-

The metal complex mentioned above is an anion, and when a salt is formed with a cation, the metal complex that is easily dissolved in water as the counter cation is preferable. Specifically, alkali metal ions such as sodium ion, potassium ion, rubidium ion, cesium ion and lithium ion, ammonium ion and alkylammonium ion are preferable. In addition to water, these metal complexes should be dissolved in a mixed solvent with an appropriate organic solvent (for example, alcohols, ethers, glycols, ketones, esters, amides, etc.) that can be mixed with water. Can do. These iridium complexes are preferably added in an amount of 1 × 10 ⁻¹⁰ mol to 1 × 10 ⁻³ mol per mol of silver during grain formation, and 1 × 10 ⁻⁸ mol to 1 × 10 ⁻⁵ mol is preferably added. Most preferred.

  In the present invention, the above-mentioned iridium complex is added directly to the reaction solution at the time of silver halide grain formation, added to an aqueous halide solution for forming silver halide grains, or to other solutions to form grains. It is preferably incorporated into the silver halide grains by adding to the reaction solution. It is also preferable to physically ripen the fine particles in which the iridium complex is previously incorporated in the grains and to incorporate them in the silver halide grains. Further, these methods can be combined and contained in the silver halide grains.

  When these complexes are incorporated into silver halide grains, they can be uniformly present inside the grains, but they are disclosed in JP-A-4-208936, JP-A-2-125245, and JP-A-3-188437. As described above, it is also preferable to be present only in the particle surface layer, and it is also preferable to add a layer containing only the complex inside the particle and not containing the complex on the particle surface. Further, as disclosed in US Pat. Nos. 5,252,451 and 5,256,530, physical ripening is performed with fine particles in which the complex is incorporated in the particles to modify the particle surface phase. It is also preferable. Further, these methods can be used in combination, and a plurality of types of complexes may be incorporated in one silver halide grain. The halogen composition at the position where the above complex is contained is not particularly limited, but the hexacoordinate complex having Ir as the central metal, in which all six ligands are Cl, Br or I, has a silver bromide concentration maximum. It is preferable to contain.

  In the present invention, it is preferable to contain a rhodium compound. More preferably, a compound represented by the following general formula (VI) is used.

General formula (VI)
[RhQnL ^I _(6-n) ] ^m
In general formula (VI), Q represents a halogen atom of chlorine, bromine or iodine, preferably a bromine atom. L ^I represents any ligand different from Br, n represents 3, 4, 5 or 6 and m preferably represents 3-, 2-, 1-, 0 or 1+. L ^I may be an organic compound be an inorganic compound, or may be even without electricity have an electric charge, but is preferably an inorganic compound. L ^I is preferably Cl, H ₂ O, NO or NS, and more preferably H ₂ O. n is preferably 5 or 6, and 6 is more preferable. m is preferably 3- or 2-, and 3- is preferred.

Although the preferable specific example of a metal complex represented with general formula (VI) below is given, this invention is not limited to these.
[RhBr ₅ Cl] ^3-
[RhBr ₆ ] ^3-
[RhBr ₅ (H ₂ O)] ^2-
[RhBr ₄ (H ₂ O) ₂ ] ⁻

  When the metal complex represented by the general formula (VI) is an anion, it is preferable that when a salt is formed with a cation, it is easily dissolved in water as a counter cation. Specifically, alkali metal ions such as sodium ion, potassium ion, rubidium ion, cesium ion and ruthenium ion, ammonium ion and alkylammonium ion are preferable. These metal complexes are used by being dissolved in a mixed solvent with water or an appropriate organic solvent (for example, alcohols, ethers, glycols, ketones, esters, amides, etc.) that can be mixed with water. be able to.

The optimum amount of these metal complexes may vary depending on the size of the silver halide grains to be contained, but it is preferable to use 5 × 10 ⁻¹⁰ moles to 1 × 10 ⁻⁷ moles per mole of silver during grain formation. More preferably, 2 × 10 ⁻¹⁰ mol to 8 × 10 ⁻⁸ mol, particularly preferably 5 × 10 ⁻¹⁰ mol to 5 × 10 ⁻⁸ mol are used.

  In the present invention, in addition to iridium and rhodium, other metal ions can be doped inside and / or on the surface of silver halide grains. As a metal ion to be used, a transition metal ion is preferable, and iron, ruthenium, osmium, lead, cadmium, or zinc is particularly preferable. Further, these metal ions are more preferably used as a hexacoordinate octahedral complex with a ligand. When an inorganic compound is used as a ligand, cyanide ion, halide ion, thiocyan, hydroxide ion, peroxide ion, azide ion, nitrite ion, water, ammonia, nitrosyl ion, or thiol It is preferable to use a nitrosyl ion, and it is also preferable to use it in coordination with any of the above metal ions of iron, ruthenium, osmium, lead, cadmium, or zinc, and a plurality of kinds of ligands are contained in one complex molecule. It is also preferable to use it. An organic compound can also be used as the ligand, and preferred organic compounds include a chain compound having 5 or less carbon atoms in the main chain and / or a 5-membered or 6-membered heterocyclic compound. . More preferable organic compounds are compounds having a nitrogen atom, a phosphorus atom, an oxygen atom or a sulfur atom in the molecule as a coordination atom to the metal, particularly preferably furan, thiophene, oxazole, isoxazole, thiazole, isothiazole. , Imidazole, pyrazole, triazole, furazane, pyran, pyridine, pyridazine, pyrimidine, and pyrazine, and compounds in which these compounds are used as a basic skeleton and substituents are introduced into them are also preferable.

A combination of metal ions and ligands is preferably a combination of iron ions, ruthenium ions and cyanide ions. In the present invention, it is preferable to use iridium and these compounds in combination. In these compounds, the cyanide ion preferably accounts for a majority of the coordination number to iron or ruthenium as the central metal, and the remaining coordination sites are thiocyanate, ammonia, water, nitrosyl ion, dimethyl sulfoxide, pyridine, It is preferably occupied by pyrazine or 4,4′-bipyridine. Most preferably, all six coordination sites of the central metal are occupied by cyanide ions to form a hexacyanoiron complex or a hexacyanoruthenium complex. These complexes containing cyanide ions as ligands are preferably added in an amount of 1 × 10 ⁻⁸ mol to 1 × 10 ⁻² mol per mol of silver during grain formation, and 1 × 10 ⁻⁶ mol to 5 × 10 5 mol. It is most preferable to add ^-4 mol. When ruthenium and osmium are used as the central metals, it is also preferable to use nitrosyl ions, thionitrosyl ions, or water molecules and chloride ions together as ligands. More preferably, a pentachloronitrosyl complex, a pentachlorothionitrosyl complex, or a pentachloroaqua complex is formed, and a hexachloro complex is also preferably formed. These complexes are preferably added in an amount of 1 × 10 ⁻¹⁰ mol to 1 × 10 ⁻⁶ mol, more preferably 1 × 10 ⁻⁹ mol to 1 × 10 ⁻⁶ mol, per mol of silver during grain formation. That is.

  In the photosensitive silver halide emulsion used in the present invention, examples of spectral sensitizing dyes used for spectral sensitization in the green and red regions include, for example, Heterocyclic compounds-Cyanine dyes and related compounds (John Wiley & Sons [New] York, London] (published in 1964). As specific examples of compounds and spectral sensitization, those described in JP-A-62-215272, page 22, right upper column to page 38 are preferably used. In particular, as a red-sensitive spectral sensitizing dye for silver halide emulsion grains having a high silver chloride content, the spectral sensitizing dye described in JP-A-3-123340 is stable, the strength of adsorption, and the exposure temperature. This is very preferable from the viewpoint of dependency and the like.

  The silver halide emulsion used in the present invention is preferably subjected to gold sensitization known in the art. For gold sensitization, various inorganic gold compounds, gold (I) complexes having inorganic ligands, and gold (I) compounds having organic ligands can be used. Examples of the inorganic gold compound include chloroauric acid or a salt thereof, and a gold (I) complex having an inorganic ligand, for example, a gold dithiocyanate such as gold (I) potassium dithiocyanate or gold (I) 3 dithiosulfate. Compounds such as gold dithiosulfate compounds such as sodium can be used.

In addition to gold sensitization, chalcogen sensitization can be performed with the same molecule, and molecules capable of releasing AuCh ⁻ can be used. Here, Au represents Au (I), and Ch represents a sulfur atom, a selenium atom, or a tellurium atom. Examples of the molecule capable of releasing AuCh ⁻ include a gold compound represented by AuCh-L. Here, L represents an atomic group constituting a molecule by bonding with AuCh. Further, one or more ligands may be coordinated with Au together with Ch-L. In addition, the gold compound represented by AuCh-L, when reacted in a solvent in the presence of silver ions, easily produces AgAuS when Ch is S, AgAuSe when Ch is Se, and AgAuTe when Ch is Te It is what has. Examples of such a compound include those in which L is an acyl group, and other examples include compounds represented by the following formula (AuCh1), formula (AuCh2), and formula (AuCh3).

Formula (AuCh1) R ₁ -X-M-ChAu
Here, Au represents Au (I), Ch represents a sulfur atom, selenium atom, tellurium atom, M represents a substituted or unsubstituted methylene group, X represents an oxygen atom, sulfur atom, selenium atom, NR ₂ R ₁ represents an atomic group (for example, an organic group such as an alkyl group, an aryl group, and a heterocyclic group) that forms a molecule by binding to X, and R ₂ represents a hydrogen atom and a substituent (for example, Represents an organic group such as an alkyl group, an aryl group, and a heterocyclic group. R ₁ and M may be bonded to each other to form a ring.
In the compound represented by the formula (AuCh1), those in which Ch is a sulfur atom and a selenium atom are preferable, X is preferably an oxygen atom and a sulfur atom, and R ₁ is preferably an alkyl group or an aryl group. Examples of more specific compounds include Au (I) salts of thiosugars (gold thioglucose such as α-gold thioglucose, gold peracetylthioglucose, gold thiomannose, gold thiogalactose, and gold thioarabinose), seleno Au (I) salts of sugars (gold peracetylselenoglucose, gold peracetylselenomannose, etc.), Au (I) salts of tellurosugar, and the like. Here, thio sugar, seleno sugar, and telluro sugar represent compounds in which the anomeric hydroxyl group of the sugar is replaced with an SH group, a SeH group, and a TeH group, respectively.

Formula (AuCh2) W ₁ W ₂ C = CR ₃ ChAu
Here, Au represents Au (I), Ch represents a sulfur atom, a selenium atom, or a tellurium atom, and R ₃ and W ₂ are substituents (for example, a hydrogen atom, a halogen atom, an alkyl group, an aryl group) W ₁ represents an electron-withdrawing group having a positive Hammett's substituent constant σp value. R ₃ and W ₁ , R ₃ and W ₂ , W ₁ and W ₂ may be bonded to each other to form a ring.
In the compound represented by the formula (AuCh2), those in which Ch is a sulfur atom and a selenium atom are preferable, R ₃ is preferably a hydrogen atom and an alkyl group, and W ₁ and W ₂ are Hammett's substituent constants σp value Is preferably an electron withdrawing group. More specific examples of the compound include (NC) ₂ C═CHSAu, (CH ₃ OCO) ₂ C═CHSAu, CH ₃ CO (CH ₃ OCO) C═CHSAu, and the like.

Formula (AuCh3) W ₃ -E-ChAu
Here, Au represents Au (I), Ch represents a sulfur atom, a selenium atom, and a tellurium atom, E represents a substituted or unsubstituted ethylene group, and W ₃ represents a positive Hammett substituent constant σp value. The value represents an electron-withdrawing group.
In the compound represented by the formula (AuCh3), Ch is preferably a sulfur atom and a selenium atom, and E is an ethylene group having an electron-withdrawing group having a positive Hammett's substituent constant σp value. W ₃ is preferably an electron-withdrawing group having a Hammett's substituent constant σp value of 0.2 or more. The amount of these compounds added may vary widely depending on the case, but is 5 × 10 ^{−7 to} 5 × 10 ⁻³ mol, preferably 3 × 10 ^{−6 to} 3 × 10 ⁻⁴ mol, per mol of silver halide. is there.

  Colloidal gold sulfide can also be used, and the manufacturing method thereof is Research Disclosure (37154), Solid State Ionics 79, 60-66, 1995, Compt. Rend.Hebt.Seances Acad.Sci.Sect.B, 263, 1328, published in 1966. The Research Disclosure describes a method using a thiocyanate ion in the production of colloidal gold sulfide, but a thioether compound such as methionine or thiodiethanol can be used instead.

Various sizes of colloidal gold sulfide can be used, those having an average particle size of 50 nm or less are preferred, average particle size of 10 nm or less is more preferred, and average particle size of 3 nm or less is even more preferred. This particle size can be measured from a TEM photograph. The composition of the colloidal gold sulfide may also Au ₂ S _1, may be of Au ₂ S ₁ ~Au ₂ S ₂ in such sulfur excess composition, sulfur excess composition is preferred. Au ₂ S _1.1 ~Au ₂ S _1.8 is more preferred.

The composition analysis of the colloidal gold sulfide can be obtained, for example, by taking out gold sulfide particles and determining the gold content and sulfur content by using an analysis method such as ICP or iodometry, respectively. If gold ions and sulfur ions (including hydrogen sulfide and its salts) dissolved in the liquid phase are present in the gold sulfide colloid, the composition analysis of the gold sulfide colloid particles will be affected. The analysis is performed after separation. The amount of colloidal gold sulfide may vary widely depending on the case, but 5 × 10 ^{−7 to} 5 × 10 ⁻³ mol, preferably 5 × 10 ^{−6 to} 5 × 10 ⁻ as gold atoms per mol of silver halide. ⁴ moles.

  In the present invention, the above gold sensitization may be combined with other sensitization methods such as sulfur sensitization, selenium sensitization, tellurium sensitization, reduction sensitization or noble metal sensitization using other than gold compounds. . It is particularly preferable to combine with sulfur sensitization and selenium sensitization.

In the present invention, a surfactant can be added to the photosensitive material from the viewpoints of improving the coating stability of the photosensitive material, preventing the generation of static electricity, and adjusting the charge amount. Examples of the surfactant include an anionic surfactant, a cationic surfactant, a betaine surfactant, and a nonionic surfactant, and examples thereof include those described in JP-A-5-333492. The surfactant used in the present invention is preferably a fluorine atom-containing surfactant. In particular, a fluorine atom-containing surfactant can be preferably used. These fluorine atom-containing surfactants may be used alone or in combination with other conventionally known surfactants, but are preferably used in combination with other conventionally known surfactants. The amount of these surfactants added to the light-sensitive material is not particularly limited, but is generally 1 × 10 ^{−5 to} 1 g / m ² , preferably 1 × 10 ⁻⁴ to 1 × 10 ^{−. 1} g / m ² , more preferably 1 × 10 ⁻³ to 1 × 10 ⁻² g / m ² .

  In addition, the photosensitive material used in the present invention includes various color couplers, polymer couplers, photographically useful group releasing couplers described in the table of paragraph 0100 of JP-A No. 2001-183778 or paragraphs 0101 to 0119, Known additives such as an oxidized developer scavenger, an anti-stain agent, an anti-fading agent, dyes, and an ultraviolet absorber can be contained.

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

  When the photosensitive material has a plurality of photosensitive layers having different spectral sensitivity distributions, and the cathode ray tube also has a phosphor that emits light in a plurality of spectral regions, a plurality of colors are exposed at a time, i.e., a plurality of cathode ray tubes Color image signals may be input to emit light from the tube surface. A method of sequentially inputting image signals for each color, causing each color to emit light sequentially, and exposing through a film that cuts colors other than that color (surface sequential exposure) may be adopted. However, since a high-resolution cathode ray tube can be used, it is preferable for improving image quality.

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

When such a scanning exposure light source is used, the spectral sensitivity maximum wavelength of the photosensitive material of the present invention can be arbitrarily set according to the wavelength of the scanning exposure light source to be used. In a solid laser using a semiconductor laser as an excitation light source or an SHG light source obtained by combining a semiconductor laser and a nonlinear optical crystal, the oscillation wavelength of the laser can be halved, so that blue light and green light can be obtained. Therefore, the spectral sensitivity maximum of the photosensitive material can be given to the usual three wavelength regions of blue, green, and red. When the exposure time in such scanning exposure is defined as the time for exposing the pixel size when the pixel density is 400 dpi, the preferable exposure time is 10 ⁻⁴ seconds or less, more preferably 10 ⁻⁶ seconds or less. For the purpose of preventing unauthorized copying of the photosensitive material subjected to the processing according to the present invention, a latent image of a microdot pattern can be given to the photosensitive material. This method is described in JP-A-9-226227.

  Preferred scanning exposure methods applicable to the present invention are described in detail in the patents listed in the table above. For processing the light-sensitive material of the present invention, page 26, lower right column, line 1 to page 34, upper right column, line 9 of JP-A-2-207250, and page 5, JP-A-4-97355. The processing materials and processing methods described in the upper left column, line 17 to page 18, lower right column, line 20 are preferably applicable.

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

EXAMPLES Hereinafter, although an Example demonstrates this invention more concretely, these do not limit the scope of the present invention at all.
(Preparation of bleaching concentrated composition)
Bleached concentrated composition samples Nos. 1 to 17 having the compositions shown in Table 1 were prepared. In addition, the quantity in a table | surface is a prescription value per 1L of compositions.
<Bleach concentrate composition>
400 ml of water
Ethylenediaminetetraacetic acid iron (III) See Table 1 Ammonium (EDTAFe (III))
Ethylenediaminetetraacetic acid (EDTA) See Table 1 m-Carboxybenzenesulfinic acid 20.0 g
Nitric acid 38.0g
Succinic acid Table 1 ammonia water (27%) 25.0g
1000ml with water
pH (25 ° C / ammonia, nitric acid adjustment) See Table 1

Nos. 1, 2, and 3, which are comparative examples in Table 1, correspond to Nos. 11, 3, and 17 in Table 2 of Example 1 of JP-A-2004-53921.
(Various performance / characteristic evaluation)
About the prepared bleaching-concentration composition samples No. 1 to 17, the following running tests were conducted using the respective bleaching-concentrating compositions, the stability of the following bleaching-concentrating compositions, and the sulfur-resistant desilvering property and silver recovery efficiency were Evaluation was performed as follows.

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

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

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

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

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

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

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

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

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

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

The coating solutions for the second to seventh layers were prepared in the same manner as the first layer coating solution. (H-1), (H-2), and (H-3) were used as gelatin hardeners for each layer. Also, Ab-1 to each layer, Ab-2, Ab-3 , and Ab-4 the total amount respectively ^{14.0mg / m 2, 62.0mg / m} 2, 5.0mg / m 2 and 10.0 mg / m It added so that it might become ² .

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

(Layer structure)
The structure of each layer is shown below. The numbers represent the coating amount (g / m ² ). The silver halide emulsion represents a coating amount in terms of silver.
Support: Polyethylene resin laminated paper [White pigment (TiO ₂ ; content: 16% by mass, ZnO; content: 4% by mass), polyethylene brightening agent (4,4′-bis (5- Methylbenzoxazolyl) stilbene (content 0.03% by mass) and bluish dye (ultraviolet, content 0.33% by mass), the amount of polyethylene resin is 29.2 g / m ² )
First layer (blue photosensitive emulsion layer)
Emulsion (5: 5 mixture of BH-1 and BL-1 (silver molar ratio)) 0.16
Gelatin 1.35
Yellow coupler (Ex-Y) 0.36
Color image stabilizer (Cpd-1) 0.01
Color image stabilizer (Cpd-2) 0.01
Color image stabilizer (Cpd-8) 0.08
Color image stabilizer (Cpd-18) 0.01
Color image stabilizer (Cpd-19) 0.02
Color image stabilizer (Cpd-20) 0.15
Color image stabilizer (Cpd-21) 0.01
Color image stabilizer (Cpd-23) 0.15
Additive (ExC-1) 0.002
Color image stabilizer (UV-A) 0.01
Solvent (Solv-4) 0.23
Solvent (Solv-6) 0.04
Solvent (Solv-9) 0.23

Second layer (color mixing prevention layer)
Gelatin 0.80
Color mixing inhibitor (Cpd-4) 0.05
Color mixing inhibitor (Cpd-12) 0.01
Color image stabilizer (Cpd-3) 0.01
Color image stabilizer (Cpd-5) 0.006
Color image stabilizer (Cpd-6) 0.05
Color image stabilizer (UV-A) 0.06
Color image stabilizer (Cpd-7) 0.006
Solvent (Solv-1) 0.06
Solvent (Solv-2) 0.06
Solvent (Solv-5) 0.07
Solvent (Solv-8) 0.07

Third layer (green photosensitive emulsion layer)
Emulsion (1: 3 mixture of GH-1 and GL-1 (silver molar ratio)) 0.10
Gelatin 0.93
Magenta coupler (ExM) 0.12
UV absorber (UV-A) 0.03
Color image stabilizer (Cpd-2) 0.01
Color image stabilizer (Cpd-6) 0.08
Color image stabilizer (Cpd-7) 0.005
Color image stabilizer (Cpd-8) 0.01
Color image stabilizer (Cpd-9) 0.01
Color image stabilizer (Cpd-10) 0.005
Color image stabilizer (Cpd-11) 0.0001
Color image stabilizer (Cpd-20) 0.01
Solvent (Solv-3) 0.06
Solvent (Solv-4) 0.12
Solvent (Solv-6) 0.05
Solvent (Solv-9) 0.16

Fourth layer (color mixing prevention layer)
Gelatin 0.63
Color mixing inhibitor (Cpd-4) 0.04
Color mixing inhibitor (Cpd-12) 0.01
Color image stabilizer (Cpd-3) 0.01
Color image stabilizer (Cpd-5) 0.005
Color image stabilizer (Cpd-6) 0.04
Color image stabilizer (UV-A) 0.05
Color image stabilizer (Cpd-7) 0.005
Solvent (Solv-1) 0.05
Solvent (Solv-2) 0.05
Solvent (Solv-5) 0.06
Solvent (Solv-8) 0.06

5th layer (red photosensitive emulsion layer)
Emulsion (4: 6 mixture of RH-1 and RL-1 (silver molar ratio)) 0.10
Gelatin 1.12
Cyan coupler (ExC-1) 0.10
Cyan coupler (ExC-2) 0.02
Cyan coupler (ExC-3) 0.02
Color image stabilizer (Cpd-1) 0.03
Color image stabilizer (Cpd-7) 0.01
Color image stabilizer (Cpd-9) 0.04
Color image stabilizer (Cpd-10) 0.001
Color image stabilizer (Cpd-14) 0.001
Color image stabilizer (Cpd-15) 0.18
Color image stabilizer (Cpd-16) 0.002
Color image stabilizer (Cpd-17) 0.001
Color image stabilizer (Cpd-18) 0.05
Color image stabilizer (Cpd-19) 0.04
Color image stabilizer (UV-5) 0.10
Solvent (Solv-5) 0.19

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

Seventh layer (protective layer)
Gelatin 0.80
Additive (Cpd-22) 0.03
Liquid paraffin 0.02
Surfactant (Cpd-13) 0.02

The sample prepared as described above was used.
2. Development processing Using the Fuji Photo Film minilab printer processor Frontier 330, the above samples were continuously processed until 3 times the amount of color developing tank solution was replenished (3 rounds) in the following processing steps and processing composition. It was. The above photosensitive material was printed with a standard negative so that the average visual density of the print would be 0.6, and was run with a processing amount of one round processing per week.

<Development processing conditions>
Processing process Temperature Time Replenishment amount Color development 38.5 ° C 45 seconds 45 ml / m ²
Bleach fixing 38.0 ° C. 25 seconds A agent 17.5 ml / m ²
Agent B 17.5 ml / m ²
Rinse (1) 38.0 ° C. 20 seconds −
Rinse (2) 38.0 ° C. 20 seconds −
Rinse (3) 38.0 ° C. 20 seconds −
Rinse (4) 38.0 ° C., 20 seconds, 175 ml / m ²
Drying 80 ° C 20 seconds * Replenishment amount per 1 m ^{2 of} photosensitive material ** Mount the rinse screening system RC50D manufactured by Fuji Photo Film Co., Ltd. on the rinse 3, take out the rinse solution from the rinse 3, and reverse osmosis module (RC50D) with a pump Send to. The permeated water sent in the tank is supplied to the rinse 4 and the concentrated solution is returned to the rinse 3. The pump pressure was adjusted so that the amount of permeated water to the reverse osmosis module was maintained at 50 to 300 mL / min, and the temperature was circulated for 10 hours per day. The rinsing was a 4-tank counterflow system from 1 to 4.

<Color developer>
[Color developer] [Tank solution] [Replenisher]
800 ml of water 800 ml
Silicon KF351A (manufactured by Shin-Etsu Chemical Co., Ltd.) 0.05g 0.05g
Potassium hydroxide 3.0g 6.0g
Sodium hydroxide 3.0g 6.0g
Optical brightener (FL-1) 0.5g 0.5g
Optical brightener (FL-2) 0.8g 0.8g
Fluorescent whitening agent (FL-3) 1.0g 1.0g
Polyethylene glycol average molecular weight 300 10.0 g 10.0 g
Diethylene glycol 10.0 g 10.0 g
Ethylenediaminetetraacetic acid 4.0 g 4.0 g
Sodium sulfite 0.10g 0.10g
Potassium chloride 10.0 g ―
4,5-dihydroxybenzene-
Sodium 1,3-disulfonate 0.50 g 0.50 g
Disodium-N, N-bis (sulfonate ethyl) hydroxylamine 4.0 g 8.0 g
m-Carboxybenzenesulfinic acid 1.5 g 2.5 g
4-Amino-3-methyl-N-ethyl-N-
(Β-Methanesulfonamidoethyl) aniline, 3/2 sulfate, monohydrate 4.0 g 12.0 g
Potassium carbonate 26.3g 26.3g
Add water for a total volume of 1000 mL 1000 mL
pH (adjusted with sulfuric acid and KOH at 25 ° C.) 10.20 12.55

  As the color developer replenisher, a 3.84 times concentrated solution was prepared in advance, which was set on the frontier 330, and was automatically diluted with water to prepare the replenisher for use.

<Bleaching fixer>
Each of the bleaching concentrated compositions described above and the following fixing concentrated composition were used after being prepared as follows. Replenisher A and B were directly replenished to the bleach-fixing tank solution for processing.
<Fixing concentration composition>
70ml water
Ammonium thiosulfate (750g / l) 500.0ml
Ammonium bisulfite solution (65%) 250.0g
15.0g of ethylenediaminetetraacetic acid
Ammonia water (27%) 45.0 g
1000ml with water
pH (25 ° C./ammonia, nitric acid adjustment) 5.75
<Tank liquid><Replenisher A agent><Replenisher B agent>
Bleached concentrated composition 250 ml 670 ml −
Fixing and Concentrating Composition 250ml-670ml
Add water 1000ml 1000ml 1000ml

<Rinse> Tank solution and replenisher common chlorinated sodium isocyanurate 0.02g
Deionized water (conductivity 5μs / cm or less) 1000ml

  In the frontier 330 used this time, when the color developing concentrated composition, the bleaching concentrated composition, and the fixing concentrated composition are set in a container for 1.3 liters for each, the concentrated composition is automatically transferred to the replenishing tank. It can be processed by diluting to the above composition with water.

<Stability of bleaching concentrated composition>
The bleached concentrated composition was prepared, put into 1300 ml of a 1300 ml polyethylene container, capped, and stored at 50 ° C. and −5 ° C. for 3 months. The sample was taken out after 3 months, and the presence or absence of deposits and liquid turbidity were visually observed. The results are shown in Table 4. The test was conducted under the conditions in order to ensure an acceleration condition of 1 year at 50 ° C. for 1 month at room temperature and to ensure long-term compensation for 3 years. The following evaluations were made step by step depending on the state of occurrence of precipitation.
○: No abnormality such as precipitation, Δ: Slight turbidity is observed, ×: Precipitation occurs,
XX: Large amount of precipitation

<Sulfurization resistance>
Using the above-mentioned bleached concentrated composition, each was subjected to 3 round running treatments according to the above-mentioned treatment method, and then the tank solution of the rinse (1) was drawn out, put into a 100 ml clear salted sun bottle, covered with a hole, and sealed. The period of time until the solution became cloudy due to aging under the condition of ° C. was evaluated and evaluated as follows.
○: No sulfidation at 4 weeks, △: Sulfidation at 4 weeks, ×: Sulfidation at 3 weeks, XX: Sulfidation at 2 weeks

<Desilvering>
Each of the bleached concentrated compositions was subjected to a three-round running process in accordance with the above processing method, a black solid sample was prepared from the photosensitive material sample, and the amount of residual silver was measured by fluorescent X-ray analysis. A large amount of residual silver is not preferable because of desilvering failure.

<Silver recovery efficiency>
The overflow solution from the bleach-fixing tank solution was collected after two rounds, and 1 liter was taken out of the overflow solution into a beaker and immersed in 500 g of steel wool, and the solution was collected after 1 hour. The silver concentration in the liquid was determined by atomic absorption analysis for the liquid in which steel wool was immersed and the percentage of silver reduced by the steel wool. Higher values mean higher silver recovery efficiency and better results.
The results obtained are shown in Table 2.

From this result, according to the present invention, the stability of the bleaching concentrated composition is improved, the sulfuration resistance and the silver recovery efficiency when running using the bleaching concentrated composition are remarkably improved, and the desilvering property is also good without any problem. It was found that good photographic quality was obtained.
In the invention of Japanese Patent Application Laid-Open No. 2004-53921, precipitation occurs at high temperatures over a long period of time and is insufficient (Nos. 1 to 3). On the other hand, if the succinic acid concentration is higher than that of the present invention, succinic acid precipitates when the concentrated solution is stored at a low temperature (No. 4). In the region where the EDTAFe (III) concentration of the present invention is low, it is presumed that the concentrated composition is likely to freeze, and that once squeezed, succinic acid is likely to precipitate significantly.
In addition, when a running treatment is performed using a concentrated composition in a region (less than 0.5 g / L) having an EDTAFe (III) concentration lower than that of JP 2004-53921 A, desilvering deterioration is observed (No. 4, No. 4). 5, 16). However, when the ratio of the free EDTA concentration is used in the concentration range of the present invention, the desilvering deterioration is eliminated.
In the visual observation, neither the edge stain nor the bleaching fog was observed in the examples of the present invention.

  Bleached concentrated composition of Example 1 A concentrated solution was prepared in the same manner except that the succinic acid of No. 9 was replaced with equimolar amounts of maleic acid, malonic acid and glutaric acid, and the stability of the concentrate was improved in the same manner as in Example 1. Examined. As a result, all of the evaluation items of the stability, sulfidation resistance, desilvering property, and silver recovery efficiency of the concentrate are good, and in the visual observation, both edge stains and bleaching fogging are recognized. There wasn't. Of these, succinic acid was found to be most preferable.

About bleaching concentration composition No9 and No11 of Example 1, it processed similarly to Example 1 except having changed into the following process conditions using the frontier 340E by Fuji Photo Film Co., Ltd.
<Development processing conditions>
Processing process Temperature Time Replenishment amount Color development 45.0 ° C 25 seconds 45 ml / m ²
Bleach fixing 40.0 ° C 25 seconds A agent 17.5ml / m ²
Agent B 17.5 ml / m ²
Rinse (1) 40.0 ° C 7 seconds-
Rinse (2) 40.0 ° C 4 seconds-
Rinse (3) 40.0 ° C 4 seconds-
Rinse (4) 40.0 ° C. 7 seconds 175 ml / m ²
Drying at 80 ° C. for 20 seconds As a result, it was found that the desilvering performance was not deteriorated in spite of rapid processing with a bleach-fixing time of 25 seconds, and good photographic performance was obtained. In addition, the frontier 340 was remodeled so that the linear velocity could be changed, the bleach-fixing time was changed, and the time allowed for desilvering performance was examined, and it was found that it could be up to 10 seconds. It was found that the cost of the treatment agent is low and rapid treatment is possible in the low region of EDTAFe (III) of the present invention. Furthermore, neither edge stain nor bleaching fog was observed in visual observation.

Claims (4)

A bleaching concentrated composition for a silver halide color photographic light-sensitive material, comprising a single solution satisfying the following compositional requirements (A) to (D).
(A) 0.10 to 0.42 mol / liter of ethylenediaminetetraacetic acid iron (III) complex salt as a bleaching agent,
(B) containing 0.5 to 30 mol% of uncomplexed ethylenediaminetetraacetic acid with respect to the bleaching agent,
(C) It contains 0.10 to 0.40 mol / liter of dibasic acid having a pKa of 2.0 to 5.0, and (D) pH is 2.0 to 3.5.   2. The bleaching concentrated composition according to claim 1, which does not contain an azole compound.   3. The bleaching concentrated composition according to claim 1 or 2, wherein the bleaching concentrated composition is diluted 1.2 to 5.0 times with water.   The bleaching concentrated composition according to any one of claims 1 to 3 and the fixing concentrated composition containing 1.0 to 3.0 mol / liter of thiosulfate are each diluted with water by 1.2 to 5.0 times. The silver halide color photographic light-sensitive material is replenished in a bleach-fixing tank at a ratio of 1: 1, and the immersion time of the silver halide photographic light-sensitive material in the bleach-fixing tank solution is 10 to 30 seconds. Material processing method.