JPH08278616A - Processing method of silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE: To decrease the fluctuation in the process when a small amt. of silver halide photosensitive material having (100) principal planar sheet like high silver chloride emulsion layer is operating, by processing the photosensitive material with a specified airtime ratio in a color developing process in an automatic developing machine. CONSTITUTION: In the processing method of a silver halide, photosensitive material having a silver halide emulsion layer satisfying the following two conditions (A), (B), the processing is carried out in such an automatic developing machine that the airtime ratio in the color developing process is <30%. (A) Planner silver halide particles having (100) plane as the principal plane and >2 aspect ratio are included by >50% of the projected area of the whole silver halide particles. (B) The average silver chloride content of the whole silver halide particles is >90mol%. Further, the processing time for the color development is <25sec. When a processing component for color development is to be replenished, it is preferable to directly supply a solid processing agent for color development to a tank for a color developing liquid.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for processing a silver halide photographic light-sensitive material.

[0002]

2. Description of the Related Art In recent years, in the photographic industry, as a part of improving the service to users, a service of returning the product within a few hours from the reception of the development is performed, and the necessity of rapid processing is increasing more and more. Furthermore, the reduction of the processing time leads to the improvement of the production efficiency and the reduction of the cost, so that the rapid processing is required.

In order to meet the current situation and needs of the market as described above, two approaches, that is, a light-sensitive material and a processing solution, have been adopted. Attempts have been made to optimize the temperature and pH of the processing liquid and to add additives such as a development accelerator. As for the light-sensitive material, there is a method of using a high silver chloride emulsion. However, although rapid processing can be carried out by these methods, it is still insufficient for the recent demands for higher speed and high image quality such as sufficient color density. Therefore, there is a demand for a silver halide photographic light-sensitive material capable of rapid processing, having high image quality, and always maintaining stable performance.

On the other hand, JP-A-6-194768, US Pat. No. 5,320,938, and European Patent No. 534395.
No. 1, a silver halide emulsion satisfying the following two conditions (hereinafter referred to as (100) principal plane tabular high silver chloride emulsion).
However, it is described that the particle shape is excellent in stability, and that it is advantageous in reducing latent image regression and sensitization.

(A) Tabular grain-shaped silver halide grains having an aspect ratio of 3 or more as the main plane of (100) plane occupy 50% or more of the projected area of all silver halide grains.

(B) The average silver chloride content of all silver halide grains is 90 mol% or more.

[0007]

However, although the (100) principal plane tabular high silver chloride emulsion is capable of rapid processing and high image quality, it can be used in a small amount during running as compared with the cubic high silver chloride emulsion. It was found that there was a large variation in processing.

An object of the present invention is to reduce the processing fluctuation of a silver halide photographic material having a (100) principal plane tabular high silver chloride emulsion layer during a small amount of running.

[0009]

The above objects of the present invention can be achieved by the following constitutions.

[1] "In a method for processing a silver halide light-sensitive material having a silver halide emulsion layer satisfying the following two conditions, an automatic processor having an air time ratio of 30% or less in a color developing step: A method of processing a silver halide photographic light-sensitive material, which comprises processing.

(A) Tabular grain-shaped silver halide grains having a (100) plane with an aspect ratio of 3 or more as the main plane occupies 50% or more of the projected area of all the silver halide grains (B) Total halogenation The average silver chloride content of silver particles is 90 mol% or more. [2] "The silver halide photographic light-sensitive material according to [1], wherein the processing time in the color developing step is 25 seconds or less. Processing method. [3] [The above-mentioned automatic processor supplies the solid processing agent for color development directly to the color development processing solution tank to replenish the processing agent component for color development [1] or [1] [2] The method for processing a silver halide photographic light-sensitive material described in [2]. [4] The method for processing a silver halide photographic light-sensitive material as described in [1], [2] or [3], which contains a magenta coupler represented by the general formula [I]. The present invention will be described in detail below. First, the (100) main plane tabular high silver chloride emulsion will be described.

The (100) principal plane tabular high silver chloride emulsion is
The tabular grain-shaped silver halide grains having an aspect ratio of 3 or more as the main plane are (100) planes occupy 50% or more of the projected area of all the silver halide grains. It is preferable that tabular grain-shaped silver halide grains whose main planes are (100) planes occupy 50% or more of the projected area of all silver halide grains,
Furthermore, a main plane with an aspect ratio of 3 or more and 20 or less is (10
It is preferable that tabular grain-shaped silver halide grains which are 0) planes account for 50% or more of the projected area of all silver halide grains.

The tabular grain-shaped silver halide grains having an aspect ratio of 3 or more (preferably 50 or less (particularly 20 or less)) whose main plane is the (100) plane are 50% or more of the projected area of all silver halide grains. Whether or not occupies 50 or more randomly selected silver halide grains has a tabular grain shape whose main plane having an aspect ratio of 3 or more (preferably 50 or less (especially 20 or less) is a (100) plane. It can be judged whether the silver halide grains occupy 50% or more of the total projected area of the silver halide grains.

The aspect ratio is the ratio of diameter to thickness of silver halide grains. The diameter of a silver halide grain means the diameter of a circle having an area equal to the projected area of the grain. The thickness of the silver halide grain is represented by the distance between two parallel planes forming the surface of the silver halide grain and having the smallest spacing. The average diameter of all silver halide grains is preferably 0.4 μm or more and 5 μm or less (particularly 3 μm or less). The average thickness of all silver halide grains is preferably 0.5 μm or less, 0.3 μm
The following is more preferable. The diameter distribution of all silver halide grains may be polydisperse or monodisperse, but monodisperse is preferable. The thickness distribution of all silver halide grains is
It may be polydisperse or monodisperse, but monodisperse is preferable.

The (100) principal plane tabular high silver chloride emulsion is
Since the average silver chloride content of all silver halide grains is 90 mol% or more, it is excellent in terms of rapid processability. And
The average silver chloride content of all silver halide grains is more preferably 95 mol% or more. Whether or not the average silver chloride content of all silver halide grains is 90 mol% or more is determined by X-ray diffraction analysis of a part of the silver halide emulsion, and It can be measured and calculated by detecting the peak and quantifying the amount of halide.

The silver halide grains of the (100) main plane tabular high silver chloride emulsion can contain silver bromide in various forms. That is, a so-called solid solution in which silver bromide is uniformly distributed may be formed in the entire silver halide grain, or a phase containing silver bromide may be nonuniformly present in the grain. When the silver bromide-containing phase is unevenly present in the grain, the silver bromide-containing phase can take various forms. For example, phases having different silver bromide contents may form a core or shell to form a so-called core / shell structure, or a phase containing a large amount of silver bromide may form inside or part of the surface of the grain. A localized phase may be formed. In the present invention, it is preferable that a silver chlorobromide phase having a high silver bromide content is localized on the grain surface from the viewpoint of high sensitivity.

The silver halide grains of the (100) principal plane tabular high silver chloride emulsion can be incorporated by adding various polyvalent metal ions in the process of grain formation or physical ripening. These various polyvalent metal ions may contain one kind of ion, or may contain plural kinds of ions in combination. Further, in order to add these various polyvalent metal ions, it is preferable to add a salt or a complex salt. Examples of these salts or complex salts include salts of cadmium, zinc, copper, thallium, gallium, or the like, or Mention may be made of salts or complex salts of Group VIII transition metal ions such as iron, ruthenium, rhodium, palladium, osmium, iridium and platinum. The amount of these various polyvalent metal ions added varies over a wide range depending on the purpose, but is preferably 10 ^-10 to 10 ^-3 mol per mol of silver halide.

The (100) main plane tabular high silver chloride emulsion is preferably chemically sensitized. Examples of the chemical sensitization method include a gold sensitization method using a gold compound (for example, US Pat. Nos. 2448060 and 3320069) or a sensitization method using a metal such as iridium, platinum or palladium (for example, US Pat. No. 2566245,
No. 2,566,263) or a sulfur sensitizing method using a sulfur-containing compound (for example, US Pat. No. 2,222,264), or a combination of two or more thereof. Specific examples of the sulfur sensitizer include thiosulfate (for example, hypo), thiourea (for example, diphenylthiourea,
Examples thereof include unstable sulfur compounds such as triethylthiourea, allylthiourea) and rhodanines, and generally about 10 ⁻⁷ to 10 ⁻² mol can be used per mol of silver halide. Specific examples of the gold sensitizer include chloroauric acid salt, chloroauric acid salt, thiocyanato gold acid salt, gold sulfide, gold selenide and the like, and generally 10 ⁻⁷ per mol of silver halide.
About 10 ^-2 mol can be used.

The (100) principal plane tabular high silver chloride emulsion is added with a dye (spectral sensitizing dye) that absorbs light in a wavelength range corresponding to the intended spectral sensitivity, and is optically added to a desired wavelength range. Can be spectrally sensitized. Examples of the spectral sensitizing dye used at this time include F.I. M. By Hamer Heterocy
CLICK COMPUNDS-Cyanine dy
es and related compounds
(John William and Sons NewYor
k, London, 1964). Examples of the spectral sensitizing dyes used include cyanine dyes, merocyanine dyes, complex merocyanine dyes, complex cyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. As the cyanine dye, simple cyanine dye, carbocyanine dye and dicarbocyanine dye are preferably used. The spectral sensitizing dye to be added may be added as it is as a crystal or a powder, but it is preferably added after being dissolved or dispersed by some method. 1 carbon atom to dissolve the spectral sensitizing dye
Alcohol, acetone, pyridine, or water-soluble solvent such as methyl cellosolve or a mixed solvent thereof may be used. In addition, micelles may be dispersed using a surfactant, or those dispersed by another dispersion method may be used. The addition amount of the spectral sensitizing dye varies widely depending on the case, but it is 1 × 10 ⁻⁶ to 1 × 1 per mol of silver halide.
It is 0 ^-2 mol, preferably 1 x 10 ^-5 to 1 x 10 ^-3 mol.

The (100) principal plane tabular high silver chloride emulsion as described above can be prepared by the method described in US Pat. No. 5,320,938 and European Patent No. 534395.

Next, the color developing process of the present invention will be described. In the present invention, processing is carried out by an automatic developing machine having an air time ratio of 30% or less in the color developing step.
The air time ratio in the color developing step is defined as the time A from the time when the silver halide light-sensitive material comes into contact with the developing solution to the time when the silver halide photosensitive material comes into contact with the processing solution in the step subsequent to the color developing step (processing time in the color developing step) A. , The time (air time) B that the silver halide light-sensitive material passes through in the air (%). In the case of the one-tank color development process, the air time ratio in the color development process is the time A from the contact of the leading edge of the silver halide photosensitive material with the developer to the contact with the processing solution of the next step of the color development process. On the other hand, the ratio of the time B until the tip of the silver halide light-sensitive material comes out of the surface of the developing solution in the color developing tank and comes into contact with the processing solution in the step subsequent to the color developing step, that is, B / A. Further, in the case of a color development process composed of a plurality of tanks, the silver halide photosensitive material is conveyed outside the processing solution until it comes out of the developing solution surface of the color developing tank and comes into contact with the developing solution of the next color developing tank. The remaining time is also included in the above-mentioned air time B.

Although the processing time of the color developing step is not limited, the present invention is particularly useful in rapid processing, and the processing time of the color developing step is preferably 1 minute or less, and particularly,
The processing time of the color development step is 25 seconds or less, which is useful and suitable.

The automatic processor may replenish the color developing treatment component by any of liquid treatment agent replenishment method, solid treatment agent replenishment method, paste treatment agent replenishment method and the like. Either a method of directly replenishing the agent to the color development processing solution tank or a method of preparing a replenishment solution from the processing agent to be replenished and replenishing the color development processing solution tank appropriately is possible. However, it is preferable to supply the solid processing agent for color development directly to the color development processing solution tank because the effects of the present invention can be better exhibited. Here, the solid developing agent for color development is a processing agent containing a solid developing agent component for color development. Examples of the form of the solid developing agent for color development include tablets, granules, powders and pills. Further, the solid developing agent for color development may be directly supplied to the color developing treatment solution tank to replenish a part of the color developing treatment agent component, but all the color developing treatment agent components are replenished. Those that do are preferred.
Further, the color development processing tank refers to all the portions where the developing solution communicates with the color development processing tank for color developing the photosensitive material, and is usually an auxiliary tank or an auxiliary tank provided in connection with the color development processing tank. A circulation path for circulating the developing solution inside and the developing solution in the color developing tank is included. Therefore, the processing agent component supplied into the color development processing solution tank is circulated, convected,
It also spreads to the developer in the color development tank due to diffusion.
Further, supplying the solid developing agent for color development directly to the color developing solution tank means supplying the solid developing agent for color developing as it is to the color developing solution tank.

Next, the magenta coupler represented by the following general formula [I] will be described.

[0025]

Embedded image

R represents a hydrogen atom or a substituent. R'represents a substituted or unsubstituted aryl group. X represents a hydrogen atom or a substituent which is released by the reaction with the oxidation product of the color developing agent.

The substituent represented by R is not particularly limited, but typical examples thereof include alkyl, aryl, anilino, acylamino, sulfonamide, alkylthio, arylthio, alkenyl and cycloalkyl groups. In addition, halogen atom and cycloalkenyl, alkynyl, heterocycle, sulfonyl, sulfinyl, phosphonyl, acyl, carbamoyl, sulfamoyl, cyano,
Of alkoxy, aryloxy, heterocycleoxy, siloxy, acyloxy, carbamoyloxy, amino, alkylamino, imide, ureido, sulfamoylamino, alkoxycarbonylamino, aryloxycarbonylamino, alkoxycarbonyl, aryloxycarbonyl, heterocyclethio Each group, a spiro compound residue, a bridged hydrocarbon compound residue, and the like are also included.

The alkyl group represented by R preferably has 1 to 32 carbon atoms and may be linear or branched. The aryl group represented by R is preferably a phenyl group.
Examples of the acylamino group represented by R include an alkylcarbonylamino group and an arylcarbonylamino group. Examples of the sulfonamide group represented by R include an alkylsulfonylamino group and an arylsulfonylamino group. The alkyl component and the aryl component in the alkylthio group and the arylthio group represented by R include the alkyl group and the aryl group represented by R. The alkenyl group represented by R is preferably one having 2 to 32 carbon atoms, and the cycloalkyl group is preferably one having 3 to 12 carbon atoms, particularly 5 to 7 carbon atoms, and the alkenyl group may be linear or branched.
The cycloalkenyl group represented by R has 3 to 10 carbon atoms.
12, especially 5 to 7, are preferred. Examples of the sulfonyl group represented by R include an alkylsulfonyl group and an arylsulfonyl group. Examples of the sulfinyl group represented by R include an alkylsulfinyl group and an arylsulfinyl group. Examples of the phosphonyl group represented by R include an alkylphosphonyl group, an alkoxyphosphonyl group, an aryloxyphosphonyl group and an arylphosphonyl group. Examples of the acyl group represented by R include an alkylcarbonyl group and an arylcarbonyl group. Examples of the carbamoyl group represented by R include an alkylcarbamoyl group and an arylcarbamoyl group. Examples of the sulfamoyl group represented by R include an alkylsulfamoyl group and an arylsulfamoyl group. Examples of the acyloxy group represented by R include an alkylcarbonyloxy group and an arylcarbonyloxy group. R
Examples of the carbamoyloxy group represented by include an alkylcarbamoyloxy group, an arylcarbamoyloxy group and the like. Examples of the ureido group represented by R include an alkylureido group and an arylureido group. Examples of the sulfamoylamino group represented by R include an alkylsulfamoylamino group and an arylsulfamoylamino group. The heterocyclic group represented by R is 5 to 7
Member is preferable, and specific examples thereof include a 2-furyl group, a 2-thienyl group, a 2-pyrimidinyl group, and a 2-benzothiazolyl group. The heterocyclic oxy group represented by R is 5 to 7
Those having a membered heterocycle are preferable, and examples thereof include a 3,4,5,6-tetrahydropyranyl-2-oxy group and a 1-phenyltetrazole-5-oxy group. The heterocyclic thio group represented by R is preferably a 5- to 7-membered heterocyclic thio group,
For example, 2-pyridylthio group, 2-benzothiazolylthio group,
2,4-diphenoxy-1,3,5-triazole-6-thio group and the like can be mentioned. Examples of the siloxy group represented by R include a trimethylsiloxy group, a triethylsiloxy group and a dimethylbutylsiloxy group. Examples of the imide group represented by R include a succinimide group, a 3-heptadecylsuccinimide group, a phthalimide group, and a glutarimide group. The spiro compound residue represented by R is spiro [3,
3] Heptan-1-yl and the like. Examples of the bridged hydrocarbon compound residue represented by R include bicyclo [2,2,1] heptan-1-yl, tricyclo [3,3,1,1 ^3.7 ] decan-1-yl,
7,7-dimethyl-bicyclo [2,2,1] heptan-1-yl and the like can be mentioned. Among the substituents represented by R, a tertiary alkyl group is preferred, and a t-butyl group is more preferred.

The substituent represented by R'is an aryl group, of which the phenyl group is preferred. Further, these groups may have a substituent.

Examples of the group which can be split off by the reaction with the oxidation product of the color developing agent represented by X include a halogen atom (chlorine atom, bromine atom, fluorine atom and the like), alkoxy, aryloxy, heterocyclic oxy, acyloxy and sulfonyl. Oxy, alkoxycarbonyloxy, aryloxycarbonyl, alkyl oxalyloxy, alkoxy oxalyloxy, alkylthio, arylthio, heterocyclic thio, alkyloxythiocarbonylthio, acylamino, sulfonamide, nitrogen-containing heterocyclic ring bonded by N atom,
Alkyloxycarbonylamino, aryloxycarbonylamino, carboxyl,

[0031]

Embedded image

(R ¹ and R ⁴ have the same meanings as R and R ′, and R ² and R ³ represent a hydrogen atom, an aryl group, an alkyl group or a heterocyclic group.) And the like. , Preferably a halogen atom, particularly a chlorine atom.

Among the magenta couplers represented by the general formula [I], preferable ones are represented by the following general formula [II].

[0034]

[Chemical 4]

In the formula, R ⁵ represents a group capable of substituting on the benzene ring, and n represents an integer of 1, 2, 3, 4 or 5. n is 2
When above, R ⁵ may be the same or different.

Examples of the group capable of substituting the benzene ring represented by R ⁵ include alkyl, cycloalkyl, alkenyl, aryl, acylamino, sulfonamide, alkylthio, arylthio, halogen atom, heterocycle, sulfonyl, sulfinyl, phosphonyl, Acyl, carbamoyl, sulfamoyl, cyano, alkoxy, aryloxy, heterocyclic oxy, siloxy, acyloxy, carbamoyloxy, amino, alkylamino, anilino, imide, ureido, sulfamoylamino, alkoxycarbonylamino, alkoxycarbonyl, aryloxycarbonyl Examples include groups such as amino and aryloxycarbonyl. Preferred among these groups are sulfonamide, sulfonyl, ureido, and alkoxy groups. Among these, a more preferable one is a sulfonamide group.

The substitutable substituent represented by R ⁵ may further have a substituent, and examples of the substituent include an alkyl group, cycloalkyl, alkenyl,
Aryl, acylamino, sulfonamide, alkylthio, arylthio, halogen atom, heterocycle, sulfonyl, sulfinyl, phosphonyl, acyl, carbamoyl, sulfamoyl, cyano, alkoxy, aryloxy, heterocycleoxy, siloxy, acyloxy, carbamoyloxy, amino, alkyl Examples thereof include amino, anilino, imide, ureido, sulfamoylamino, alkoxycarbonylamino, alkoxycarbonyl, aryloxycarbonylamino and aryloxycarbonyl groups. Among these groups, preferred groups are sulfonamide, sulfonyl and the like.

Typical examples of the magenta coupler represented by the general formula [I] are shown below, but the invention is not limited thereto.

[0039]

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[0040]

[Chemical 6]

[0041]

[Chemical 7]

[0042]

Embedded image

The silver halide photographic light-sensitive material according to the present invention has absorption in various wavelength regions for the purpose of preventing irradiation, halation and improving safety of safelight, for example, EP No. 27,490 of European Patent EP 337490A2.
It is preferable to add dyes (oxonol dyes, cyanine dyes) that can be decolorized by the treatment described on pages 76 to 76.

A silver halide light-sensitive material having a (100) main plane tabular high silver chloride emulsion layer can form an image by performing color development processing known in the art, but it is supplemented with a color development processing agent component. However, it is preferable to directly supply the solid developing agent for color development to the color development processing bath.

[0045]

【Example】

Example 1 [Preparation of emulsion] (Preparation of blue-sensitive emulsion) 1000 ml of a 2% gelatin aqueous solution kept at 40 ° C contained 25 ml of an aqueous solution containing 2.86 g of sodium chloride and 119 mg of potassium bromide, and 8.5 g of silver nitrate. 20 ml of the aqueous solution was added to pAg6.5
Simultaneous addition was performed over 30 minutes while controlling the pH to 3.0. Furthermore, sodium chloride 54.4 g and potassium bromide 2.2
6 g, potassium hexachloroiridium (IV) acid 0.0
270 ml of an aqueous solution containing 24 mg, and silver nitrate 16
270 ml of an aqueous solution containing 1.4 g was added to pAg7.3 · p
Simultaneous addition was carried out over 120 minutes while controlling to H5.5.

After the addition was completed, a precipitating agent (Kao Atlas Co., Ltd.)
5% aqueous solution of DEMOL N and 20% of magnesium sulfate
It was desalted with an aqueous solution. Then, it was washed with water and mixed with an aqueous gelatin solution to prepare a cubic silver chlorobromide emulsion EM-1 (average particle size 0.7 μm, coefficient of variation of particle size distribution (standard deviation of particle size / average particle size) 0.07, An average silver chloride content of 98 mol%) was obtained.

The following compounds were used for the above EM-1 to adjust the pH.
Optimal chemical sensitization was performed at 6.0.62 ° C. to obtain a blue-sensitive silver halide emulsion EMB-1.

Addition amount of compound Sodium thiosulfate 0.8 mg / AgX mole Chloroauric acid 0.5 mg / AgX mole Stabilizer (STAB-3) 8 × 10 ⁻⁴ mole / AgX mole Sensitizing dye (BS-1) 4 × 10 ⁻⁴ mol / AgX mol Sensitizing dye (BS-2) 1 × 10 ⁻⁴ mol / AgX mol (Preparation of green-sensitive emulsion 1) 1000 ml of 2% gelatin aqueous solution kept at 40 ° C. and 2.86 g of sodium chloride 25 ml of an aqueous solution containing 119 mg of potassium bromide, and
20 ml of an aqueous solution containing 8.5 g of silver nitrate was added to pAg6.5
-While controlling to pH 3.0, it added simultaneously over 30 minutes.
Furthermore, sodium chloride 19.8 g and potassium bromide 0.
87 g, potassium hexachloroiridium (IV) ate 0.
99 ml of an aqueous solution containing 0087 mg, and silver nitrate 5
90 ml of an aqueous solution containing 3.4 g has a pAg of 7.3.pH.
Simultaneous addition was carried out over 40 minutes while controlling at 5.5.

After the addition was completed, a precipitating agent (Kao Atlas Co., Ltd.)
5% aqueous solution of DEMOL N and 20% of magnesium sulfate
It was desalted with an aqueous solution. Thereafter, it was washed with water and mixed with an aqueous gelatin solution to obtain a cubic silver chlorobromide emulsion (average grain size 0.5 μm, variation coefficient of grain size distribution (standard deviation of grain size / average grain size) 0.07, Emulsion EM-2 having an average silver chloride content of 98 mol%) was obtained.

Next, EM-2 was optimally chemically sensitized at 60 ° C. using the following compound to obtain a green-sensitive silver halide emulsion EMG-1.

Addition amount of compound Sodium thiosulfate 3.0 mg / AgX mol Stabilizer (STAB-1) 6 × 10 ⁻⁴ mol / AgX mol Stabilizer (STAB-2) 3 × 10 ⁻⁴ mol / AgX mol Sensitizing dye (GS-1) 4 × 10 ⁻⁴ mol / AgX mol (Preparation of green-sensitive emulsion 2) Low methionine gelatin 3.5%, 5.6 mM sodium chloride and 0.15 mM in a reaction vessel.
Keep 2 liters of potassium iodide aqueous solution at 40 ℃, 2M
30 ml of an aqueous silver nitrate solution and 30 ml of an aqueous solution of 1.99 M sodium chloride and 0.01 M potassium iodide were simultaneously added at 60 ml / min each. And it stirred for 10 minutes. After that, 1266 ml of 0.5 M silver nitrate aqueous solution was added,
After adding at 5.0 ml / min for 84 minutes, set the flow rate to 15.0.
The addition was made in ml / min for 56 minutes. At this time, 0.5M sodium chloride solution containing 0.0087 mg of potassium hexachloroiridium (IV) ate was simultaneously added to maintain pCl at a constant value of 2.32.

A precipitating agent (5% aqueous solution of Demol N manufactured by Kao Atlas Co., Ltd.) and magnesium sulfate 2 was added to the obtained emulsion.
0% aqueous solution) was added for precipitation. After that, desalination washing,
By mixing with an aqueous gelatin solution, an emulsion EM-3 having a gelatin amount of about 45 g / mol was obtained. In this emulsion, tabular grain-shaped silver halide grains having an aspect ratio of 3 or more as the principal plane of (100) plane account for 70% of the projected area of all silver halide grains.
Occupied. The average diameter of all silver halide grains was 1.03 μm, and the average thickness was 0.12 μm. The average silver chloride content of all silver halide grains is 99.6.
It was mol%.

EM-3 was optimally chemically sensitized at 60 ° C. using the same compound as in the preparation of EMG-1. This emulsion was designated as EMG-2.

(Preparation of Red-Sensitive Emulsion) EM-2 was optimally chemically sensitized with the following compound at 65 ° C. to obtain a red-sensitive silver halide emulsion EMR-1.

Amount of compound added Sodium thiosulfate 1.8 mg / AgX mol Chloroauric acid 2.0 mg / AgX mol Stabilizer (STAB-1) 6 × 10 ⁻⁴ mol / AgX mol Stabilizer (STAB-2) 3 × 10 ^-4 mol / AgX mol Sensitizing dye (RS-1) 1 × 10 ⁻⁴ mol / AgX mol Sensitizing dye (RS-2) 1 × 10 ⁻⁴ mol / AgX mol STAB-1: 1- (3-acetamide Phenyl) -5
-Mercaptotetrazole STAB-2: 1-phenyl-5-mercaptotetrazole STAB-3: 1- (4-ethoxyphenyl) -5-mercaptotetrazole [Preparation of sample] On a paper support coated on both sides with polyethylene Then, each layer having the following constitution was coated to prepare a photosensitive material sample 1. The coating liquid was prepared as follows.

First layer coating liquid Compound addition amount Yellow coupler (Y-1) 23.4 g Dye image stabilizer (ST-1) 3.34 g (ST-2) 3.34 g (ST-5) 3.34 g Anti-staining agent (HQ-1) 0.33 g Compound A 5.0 g High boiling point organic solvent (DBP) 5.0 g Ethyl acetate 60 ml was added and dissolved, and this solution was dissolved in 20% surfactant (SU-
1) 220 ml of 10% gelatin aqueous solution containing 7 ml
A yellow coupler dispersion was prepared by emulsifying and dispersing with an ultrasonic homogenizer. This dispersion was mixed with a blue-sensitive silver halide emulsion prepared under the following conditions to prepare a first coating solution. The coating liquids for the second to seventh layers were prepared in the same manner as the coating liquid for the first layer so that the coating amounts were as shown in Tables 1 and 2.

Further, as a hardener (H-1), (H-2)
Was added. As a coating aid, a surfactant (SU-
2) and (SU-3) were added to adjust the surface tension.
Further, F-1 was added to each layer so that the total amount was 0.04 g / m ² .

[0058]

[Table 1]

[0059]

[Table 2]

SU-1: Sodium tri-i-propylnaphthalene sulfonate SU-2: Di (2-ethylhexyl) sulfosuccinate / sodium salt SU-3: Di (2,2,3,3,4) sulfosuccinate , 4,5,5-Octafluoropentyl) -sodium salt DBP: dibutylphthalate DNP: dinonylphthalate DOP: dioctylphthalate DIDP: di-i-decylphthalate PVP: polyvinylpyrrolidone H-1: tetrakis (vinylsulfonylmethyl) methane H-2: 2,4-dichloro-6-hydroxy-s-triazine
Sodium HQ-1: 2,5-di-t-octylhydroquinone HQ-2: 2,5-di-sec-dodecylhydroquinone HQ-3: 2,5-di-sec-tetradecylhydroquinone HQ-4: 2- sec-dodecyl-5-sec-tetradecyl hydroquinone HQ-5: 2,5-di (1,1-dimethyl-4-hexyloxycarbonyl) butyl hydroquinone

[0061]

[Chemical 9]

[0062]

[Chemical 10]

[0063]

[Chemical 11]

[0064]

[Chemical 12]

[0065]

[Chemical 13]

[0066]

Embedded image

The third layer EMG-1 of Sample 1 was replaced with EMG-2.
Sample 2 was prepared in the same manner as Sample 1 except that the above was changed to. The sample prepared in this manner was used as a Konica NPS81
It was rated at 8.

The method for adjusting the airtime ratio is shown below.

FIG. 1 is a model diagram of a transfer rack from the processing tank to the next tank in the color developing process. FIG. 1A is a sectional view of a processing tank and a transfer rack, and FIG. 1B is a perspective view thereof.
The transfer rack 50 has three sets of opposed squeeze rollers 51, which convey the photosensitive material along a guide 52 which guides the photosensitive material 53. The adjustment of the air time ratio is performed by adjusting the track length of the guide material 52 through which the photosensitive material passes.
It was performed by adjusting as in (a), (c), and (d). That is, the squeeze rollers facing each other were set in three sets even if the track length was changed, and the pressure-bonding properties were made the same. Then, the airtime ratio was adjusted by adjusting the length of the processing rack.

The development processing steps and the constitution of the development processing solution are shown below.

Treatment process Treatment Temperature Time Replenishment amount Color development 38.0 ± 0.3 ℃ 45 seconds 80cc Bleach fixing 35.0 ± 0.5 ℃ 45 seconds 120cc Stabilization 30-34 ℃ 60 seconds 150cc Dry 60-80 ℃ 30 seconds Development processing The composition of the liquid is shown below.

Color developer tank solution and replenisher tank solution Replenisher pure water 800cc 800cc triethylenediamine 2g 3g diethylene glycol 10g 10g potassium bromide 0.01g-potassium chloride 3.5g-potassium sulfite 0.25g 0.5g N-ethyl-N- ( β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate 6.0g 10.0g N, N-diethylhydroxylamine 6.8g 6.0g triethanolamine 10.0g 10.0g diethylenetriaminepentaacetic acid sodium salt 2.0g 2.0g fluorescence Whitening agent (4,4'-diaminostilbene disulfonic acid derivative) 2.0g 2.5g Potassium carbonate 30g 30g Add water to bring the total volume to 1 liter. Adjust the tank solution to pH = 10.10 and the replenisher to pH = 10.60. To do.

Bleach-fix solution tank replenisher and replenisher diethylenetriamine pentaacetate ammonium ferric dihydrate 65 g diethylenetriamine pentaacetic acid 3 g ammonium thiosulfate (70% aqueous solution) 100 cc 2-amino-5-mercapto-1,3,4-thiadiazole 2.0 g Ammonium sulfite (40% aqueous solution) 27.5cc Add water to make the total volume 1 liter, and adjust the pH to 5.0 with potassium carbonate or glacial acetic acid.

Stabilizing solution tank solution and replenishing solution o-phenylphenol 1.0 g 5-chloro-2-methyl-4-isothiazolin-3-one 0.02 g 2-methyl-4-isothiazolin-3-one 0.02 g diethylene glycol 1.0 g Optical brightener (Tinopearl SFP) 2.0 g 1-hydroxyethylidene-1,1-diphosphonic acid 1.8 g Bismuth chloride (45% aqueous solution) 0.65 g Magnesium sulfate heptahydrate 0.2 g PVP 1.0 g Ammonia water (ammonium hydroxide 25 % Aqueous solution) 2.5 g nitrilotriacetic acid trisodium salt 1.5 g Add water to make the total volume 1 liter, and adjust the pH to 7.5 with sulfuric acid or aqueous ammonia.

With the above replenishing method, continuous processing of 7.5 m ² of color paper per day was carried out for 2 weeks, and the processing fluctuation due to a small amount of running, development unevenness, and sensitivity were evaluated as follows.

<Processing Variation> During the running experiment, each light-sensitive material sample (control strip) subjected to wedge exposure by a conventional method was processed once a day to obtain the maximum green light reflection density (D
_max ) and gradation (characteristic curve green light reflection density 0.5 and 1.
(Gradient connecting 5) (γ) and minimum green light reflection density (D _min )
X-rite 310 densitometer (manufactured by X-rite Co., Ltd.)
And the difference between the maximum value and the minimum value was defined as the processing variations ΔD _max , Δγ, and ΔD _min in the small amount running.

<Development unevenness> After completion of the small amount running experiment,
Each photosensitive material sample was processed, and the occurrence of streak unevenness was visually evaluated, and the occurrence of streak unevenness is shown by the number per 10 m ² .
The results are shown in Table 3.

<Sensitivity> The sample was wedge-exposed with white light for 0.5 seconds, and then developed by each processing method of the examples. The sensitivity was calculated by the reciprocal of the exposure amount required to give a density of 0.8 higher than the fog density in the reflection density of the prepared processed sample. The sensitivity of 1 is 100 and each experiment is N
o. Was evaluated as a relative value.

[0079]

[Table 3]

As is clear from Table 3, the silver halide photographic light-sensitive material having the (100) main plane tabular high silver chloride emulsion layer has an air time ratio of 30 in the color development step as compared with a light-sensitive material which does not have such a silver halide photographic light-sensitive material. When the processing exceeds%, the processing fluctuation is large. However, the airtime ratio in the color development process is 3
When the treatment amount was 0% or less, the process variation due to running was small even in the small amount treatment, the development unevenness was small, and the sensitivity was high.

Example 2 The sample used in Example 1 was developed with NPS818 manufactured by Konica Corp. by the same replenishment method as in Example 1 at the processing time and air time ratio of the color development step shown in Table 4. did. The results are shown in Table 4.

[0082]

[Table 4]

As is clear from the comparison between Table 3 and Table 4, in the comparative example, when the processing time of the color developing step is 25 seconds or less, the processing variation becomes large, the development unevenness increases, and the sensitivity decreases. To do However, in the combination of the present invention, even if the processing time of the color development step is 25 seconds or less, as in Example 1, there is little processing variation due to running even when processing a small amount, uneven development is small, and high sensitivity is obtained. There is no change.

Example 3 Next, a system for directly supplying and supplementing the solid processing agent to the color development processing tank was also carried out. Implementation in this system is Japanese Patent Application No. 6-16538.
The automatic processing machine described in the example of No. 8 was used, and the solid processing agent was prepared and treated by the method described in the patent. In this embodiment, the conventional replenishing solution replenishing method for NPS818 manufactured by Konica Corporation was set as replenishing method A, and the solid processing agent supply method was set as replenishing method B. The sample used in Example 1 was subjected to the color development time, air time ratio and replenishment method shown in Table 5. The results are shown in Table 5.

[0085]

[Table 5]

As is clear from Table 5, in the combination of the present invention, by adopting the replenishing method B, the processing fluctuation due to running can be further reduced even when processing a small amount, and development unevenness can be further prevented.

Example 4 Samples 3 to 6 were prepared in the same manner as Samples 1 and 2 except that M-1 of the third layer of Samples 1 and 2 of Example 1 was changed as shown in Table 6. did. Samples 1-6 were processed in replenishment mode B as in Example 3. The results are shown in Table 6.

[0088]

[Table 6]

As is clear from Table 6, in the combination of the present invention in which the magenta coupler is changed to the magenta coupler represented by the above-mentioned general formula [I], the processing variation due to running is small and the development unevenness is small. High sensitivity.

[0090]

【The invention's effect】

[Brief description of drawings]

FIG. 1 is a schematic configuration diagram of a transfer rack from a color development processing tank to a next tank.

[Explanation of symbols]

 50 Crossing Rack 51 Squeeze Roller 52 Guide Guide 53 Photosensitive Material

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Office reference number FI technical display location G03D 3/00 G03D 3/00 Z

Claims (4)

[Claims] 1. A silver halide light-sensitive material having a silver halide emulsion layer satisfying the following two conditions is processed by an automatic processor having an air time ratio of 30% or less in a color development step. A method for processing a silver halide photographic light-sensitive material. (A) A tabular grain-shaped silver halide grain having a (100) plane with an aspect ratio of 3 or more as the main plane occupies 50% or more of the projected area of all the silver halide grains. (B) Of all the silver halide grains The average silver chloride content is 90 mol% or more 2. The method of processing a silver halide photographic light-sensitive material according to claim 1, wherein the processing time of the color developing step is 25 seconds or less. 3. The automatic developing machine supplies the color developing solid processing agent directly to the color developing processing solution tank to replenish the color developing processing agent component. The method for processing a silver halide photographic light-sensitive material described in 1. 4. A magenta coupler represented by the following general formula [I] is contained, wherein the magenta coupler is contained.
The method for processing a silver halide photographic light-sensitive material described in 1. Embedded image R represents a hydrogen atom or a substituent. R'represents a substituted or unsubstituted aryl group. X represents a hydrogen atom or a substituent which is released by the reaction with the oxidation product of the color developing agent.