JP3496778B2 - Silver halide photographic light-sensitive material and processing method thereof - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic light-sensitive material and a method for processing the same, and particularly to use in a small automatic processor processing system for medical radiography or an extremely low waste liquid processing system. And a processing method thereof.

[0002]

2. Description of the Related Art In recent years, there has been a strong demand in the medical field to reduce the amount of processing waste liquid from the viewpoint of environmental protection and space saving.
Therefore, it is necessary to increase the activity of the processing liquid, and there has been a history of increasing the amount of the developing agent and auxiliary developing agent in the developing solution and increasing the pH of the developing solution. However, in general, when the activity of the developer is increased, it is likely to be oxidatively deteriorated and the processing stability is deteriorated. Therefore, it is considered that there is a limit to the improvement of only the developer for extremely low replenishment and low waste of the developer. Further, there is already known a technique of using ascorbic acid as a new developing agent in place of hydroquinone which has been conventionally used as a developing agent for black and white development. Specifically, JP-A-4
-270343, JP-A-6-019069 and the like. A photosensitive material having a high processing stability suitable for such a replenishment of the developer and a new developer is desired. By the way, in a processing system using an automatic developing machine, rapid processing, downsizing of the automatic developing machine, and reduction in power consumption are strongly desired from the past. The method of evaporating water with hot air is generally used to dry the washed sensitive material, but increasing the hardness of the sensitive material and keeping the water content at the time of washing low will dry the sensitive material quickly. It is advantageous in that However, when the film hardness of the light-sensitive material is increased, the photographic performance of the light-sensitive material is remarkably deteriorated in the processing method described above, and the sensitivity is lowered, and softening occurs due to insufficient development in the high density region. There was such a problem.

[0003]

[SUMMARY OF THE INVENTION Therefore, to provide a rapid and / or good photographic performance is obtained even in a developing solution processing very low replenishment and treatment method of drying is good photographic material Is.

[0004]

The objects of the present invention have been achieved by the following means. (1) A photographic light-sensitive material having at least one photosensitive silver halide emulsion layer coated on at least one side of a support, wherein the amount of coated silver is 0.5 g / m 2 on at least one side of the support. ² or more and 1.5 g / m ² or less, and the emulsion layer
50% of the projected area of silver halide grains contained in
Flat plate with aspect ratio of 3 to 30
-Like silver halide grains,
The average value of the equivalent circle diameter of the projected area is 0.1 micron or more.
It is 8 microns or less, and the photosensitive silver halide grains in the emulsion layer are sensitized with a selenium compound, and the swelling rate of the entire hydrophilic colloid layer on the emulsion layer side of the photographic light-sensitive material is 130% or more and 200% or more. % or less der Ru silver halide photographic light-sensitive
The optical material is represented by the following general formula (I) by an automatic processor.
Substantially polyhydroxybenzenes containing a developing agent
Development time of 5 seconds or more and 30 seconds or less with a compound-free developer
A silver halide photographic texture characterized by being developed under
Optical material processing method.

[0005]

[Chemical formula 1]

In the general formula (I), R1 and R2 are
Hydroxyl group, amino group, mercapto group or
Represents an alkylthio group. P and Q are hydroxyl
Group, carboxyl group, alkoxy group, hydroxyalk
Group, carboxyalkyl group, sulfo group, sulfoalkyl group
Group, amino group, alkyl group, or aryl group
Or P and Q are bound to each other and R1 and R2 are substituted
The two vinyl carbon atoms and the carbon substituted by Y
Represents a group of atoms forming a 5- to 8-membered ring with atoms. Y is
Represents = 0 or = N-R3. R3 is hydrogen atom, hydr
Roxyl group, alkyl group, acyl group, sulfoalkyl group
Alternatively, it represents a carboxyalkyl group.

(2) The method of processing a silver halide photographic light-sensitive material according to (1), wherein the silver halide photographic light-sensitive material has a layer containing a non-eluting conductive substance.

[0008]

[0009]

(3) The replenishment amount of the developing solution is 25 ml or more and 200 ml or less per 1 m ^{2 of the} light-sensitive material.
The method for processing a silver halide photographic light-sensitive material according to (1) or (2) . The present invention will be described in detail below. In the present invention, the coated silver amount per one side of the support is 0.5 g /
m ² or more and 1.5 g / m ² or less, 1.0 g / m ² or more 1.
45 g / m ² or less is more preferable, and 1.2 g / m ² or more is 1.
Most preferably 4 g / m ² or less.

The silver halide photographic light-sensitive material of the present invention (hereinafter, simply referred to as a light-sensitive material) is preliminarily hardened by adding a hardener to the coating solution to crosslink the gelatin in the hydrophilic colloid layer. ing. In the light-sensitive material of the present invention, the swelling ratio is 130% or more and 200% or less, but 140% or more 1
90% or less is more preferable, and 150% or more and 180% or less is the most preferable. The swelling ratio in the present invention means Japanese Patent Laid-Open No. 58-58
It is based on the same definition as described in No. 111933.

As the selenium sensitizer used in the present invention, the selenium compounds disclosed in conventionally known patents can be used. That is, usually, an unstable selenium compound and / or a non-unstable selenium compound is added,
It is used by stirring the emulsion at a high temperature, preferably 40 ° C. or higher for a certain time. Unstable selenium compounds are disclosed in JP-B-44-15748 and JP-B-43-13489.
JP-A-2-130976, JP-A-4-10924
It is preferable to use the compounds described in No. 0 and the like. Specific examples of unstable selenium sensitizers include isoselenocyanates (eg, aliphatic isoselenocyanates such as allyl isoselenocyanate), selenoureas, selenoketones, selenamides, selenocarboxylic acids (eg,
2-selenopropionic acid, 2-selenobutyric acid), selenoesters, diacyl selenides (for example, bis (3-chloro-2,6-dimethoxybenzoyl) selenide), selenophosphates, phosphine selenides, bis (oxycarbonyl) ) Selenides, colloidal metal selenium and the like. Specific examples of preferred selenium compounds used in the present invention are shown below, but the present invention is not limited thereto.

[0013]

[Chemical 2]

[0014]

[Chemical 3]

[0015]

[Chemical 4]

[0016]

[Chemical 5]

[0017]

[Chemical 6]

[0018]

[Chemical 7]

[0019]

[Chemical 8]

[0020]

[Chemical 9]

These selenium sensitizers are dissolved in water or an organic solvent such as methanol or ethanol, alone or in a mixed solvent, or disclosed in JP-A-4-140738 and JP-A-4-140738.
No. 140739 is added at the time of chemical sensitization. It is preferably added before the start of chemical sensitization. The selenium sensitizer used is not limited to one type, and two or more types of the above selenium sensitizers can be used in combination. The unstable selenium compound and the non-unstable selenium compound may be used in combination. The addition amount of the selenium sensitizer used in the present invention varies depending on the activity of the selenium sensitizer used, the type and size of silver halide, the temperature and time of ripening, and the like. It is 1 × 10 ⁻⁸ mol or more per mol. It is more preferably 1 × 10 ⁻⁷ mol or more and 1 × 10 ⁻⁵ mol or less. The temperature of chemical ripening when a selenium sensitizer is used is preferably 45 ° C. or higher. More preferably 50 ° C or higher 8
It is 0 ° C or lower. pAg and pH are arbitrary. For example, the effect of the present invention can be obtained in a wide range of pH from 4 to 9. It is more effective to perform selenium sensitization in the presence of a silver halide solvent.

As the silver halide solvent which can be used in the present invention, US Pat. Nos. 3,271,157, 3,531,289, 3,574,628 and JP-A-54- (A) Organic thioethers described in 1019, 54-158917 and the like, JP-A-53-824.
No. 08, No. 55-77737, No. 55-2982 and the like (b) thiourea derivatives, JP-A-53-144
(C) a silver halide solvent having a thiocarbonyl group sandwiched between an oxygen or sulfur atom and a nitrogen atom, and (d) described in JP-A No. 54-100717.
Examples thereof include imidazoles, (e) sulfite, (f) thiocyanate and the like. Particularly preferred solvents are thiocyanate and tetramethylthiourea. The amount of the solvent used varies depending on the kind, but in the case of thiocyanate, the preferable amount is 1 per mol of silver halide.
It is not less than × 10 ^-4 mol and not more than 1 × 10 ^-2 mol.

The silver halide emulsion of the present invention can achieve higher sensitivity and lower fog by combined use of sulfur sensitization and / or gold sensitization in chemical sensitization. Sulfur sensitization is usually carried out by adding a sulfur sensitizer and stirring the emulsion at a high temperature, preferably 40 ° C. or higher for a certain period of time. The gold sensitization is usually carried out by adding a gold sensitizer and stirring the emulsion at a high temperature, preferably 40 ° C. or higher for a certain time. For sulfur sensitization, known sulfur sensitizers can be used. For example, thiosulfate, thioureas, allylisothiocyanate, cystine, p-toluenethiosulfonate,
Examples include rhodanine. Other US Patent No. 1,5
74,944, 2,410,689, 2,
278,947, 2,728,668, 3,501,313, 3,656,955, German Patent 1,422,869, Japanese Patent Publication No. 56-
The sulfur sensitizers described in JP-A-24937, JP-A-55-45016 and the like can also be used. The sulfur sensitizer may be added in an amount sufficient to effectively increase the sensitivity of the emulsion. This amount varies over a considerable range under various conditions such as pH, temperature, and large size of silver halide grains, but it is 1 × 10 ^-7 mol or more and 5 × 10 ^-4 mol per mol of silver halide. The following are preferred.

As the gold sensitizer for the above-mentioned gold sensitization, the oxidation number of gold may be +1 valence or +3 valence, and a gold compound usually used as a gold sensitizer can be used. Typical examples are chloroauric acid salt, potassium chloroaurate, auric trichloride, potassium auric thiocyanate, potassium iodoaurate, tetracyanoauric acid, ammonium aurothiocyanate ,. Pyridyl trichloro gold etc. are mentioned. The amount of the gold sensitizer added varies depending on various conditions, but as a guide, it is preferably 1 × 10 ^{−7 to} 5 × 10 ⁻⁴ mol per mol of silver halide. At the time of chemical ripening, it is not necessary to particularly limit the timing and order of addition of a silver halide solvent and a selenium sensitizer or a sulfur sensitizer and / or a gold sensitizer which can be used in combination with a selenium sensitizer. Alternatively, for example, the above compounds can be added at the same time as the initial (preferably) chemical ripening or during the progress of chemical ripening, or at different addition points. In addition, at the time of addition, the above compound may be dissolved in water or an organic solvent capable of mixing with water, for example, a single liquid or a mixed liquid of methanol, ethanol, acetone or the like and added.

When the selenium sensitizer and the sulfur sensitizer are used in combination, the addition amount is 1: 9 to 9: in a molar ratio of 1 equivalent of selenium and sulfur.
1 is preferred. Particularly, 5: 5 to 7: 3 is more preferable.

The silver halide emulsion used in the silver halide photographic light-sensitive material of the present invention includes any of silver chloride, silver chlorobromide, silver chloroiodide, silver chloroiodobromide, silver bromide, silver iodobromide and the like. However, silver iodobromide is preferred from the viewpoint that high sensitivity can be obtained, and silver chloride and silver chlorobromide are preferred from the viewpoint of good fixability. To be Particularly, the silver iodide content is 0 mol% or more 1
It is preferably not more than mol%. For the silver halide emulsion preferably used in the present invention, the average circle equivalent diameter of the projected areas of the silver halide grains is calculated as the average value of all the silver halide grains. The average circle equivalent diameter is preferably 0.
It is not less than 1 micron and not more than 1.2 micron, but especially 0.
It is more preferably 1 micron or more and 0.8 micron or less, and most preferably 0.5 micron or more and 0.7 micron or less.

The silver halide grains in the silver halide emulsion may be isotropically grown grains such as cubes, octahedra and tetradecahedrons, or may be polyhedral grains such as spheres, or may be parallel grains. It may be a tabular grain having twin planes and having a (111) plane as a main plane, or a tabular grain having a (100) plane as a main plane. In particular, have twin planes parallel to each other (10
A tabular grain having a (0) plane as a main plane or a tabular silver halide grain having a (100) plane as a main plane is preferably used. The tabular silver halide grains preferably used in the present invention will be described in detail. The thickness of the tabular silver halide grains is preferably 0.05 micron or more and 0.2 micron or less, and 0.08 micron or more and 0.16 or more.
More preferably, it is 0.1 micron or more and 0.1 micron or less.
Most preferred is 15 microns or less. The aspect ratio of a tabular silver halide grain is defined as the value obtained by dividing the equivalent circle diameter of the projected area of one grain by the thickness of the grain, and the average aspect ratio of all grains is preferably 2 or more and 20 or less, and particularly preferably 4 or more and 10 or less are more preferable, and further 5
The range of 8 or less is most preferable in that the silver tone is good and the optical density per unit developed silver amount is high. The proportion of tabular silver halide grains having an aspect ratio of 3 or more and 30 or less is preferably such that the sum of projected areas thereof is 50% or more and 100% or less with respect to the sum of projected areas of all grains, and more preferably 70% or more. 100% or less, most preferably 90
% Or more and 100% or less.

The method for producing tabular silver halide grains is as follows:
This can be achieved by appropriately combining methods known in the art. In addition, while forming a seed crystal in which tabular grains are present in an amount of 40% or more by weight in an atmosphere having a relatively low pBr value of pBr 1.3 or less, while simultaneously maintaining the same pBr value and adding a silver and halogen solution at the same time, Obtained by growing seed crystals. During this grain growth process, it is desirable to add silver and halogen solutions so that new crystal nuclei are not generated. The size of the tabular silver halide grains can be controlled by controlling the temperature,
It can be adjusted by selecting the kind and amount of the solvent, controlling the addition rate of the silver salt used during grain growth, and the halide. Further, in the present invention, among the tabular silver halide grains, monodisperse hexagonal tabular grains are particularly useful grains. The details of the structure and manufacturing method of the monodisperse hexagonal tabular grains are as described in JP-A-63-151618.

The silver halide emulsion preferably used in the present invention may have a uniform crystal structure, but may have a different halogen composition inside and outside, or may have a layered structure. Further, it is preferable that reduction sensitized silver nuclei are contained during grain formation. In the present invention, so-called halogen conversion type (conversion type) particles as described in British Patent 635,841 and US Pat. No. 3,622,318 can be used particularly effectively. Halogen conversion is 0.2mol% to 2mo with respect to silver.
1% is preferable, and 0.2 mol% to 0.6 mol% is particularly preferable. In the silver iodobromide emulsion, grains having a structure having a high iodine layer inside and / or on the surface thereof are particularly preferable. Further, by converting the surface of tabular silver halide grains preferred in the present invention to a high iodine type, a silver halide emulsion having higher sensitivity can be obtained. The silver halide composition on the grain surface before conversion to halogen is preferably an iodine content of 1 mol% or less. Especially 0.4mo
It is preferably 1% or less. A method in which a silver halide solvent is present when halogen conversion is performed by the above method is particularly effective. Preferred solvents include thioether compounds, thiocyanates and 4-substituted thioureas. Among them, the thioether compound and the thiocyanate are particularly effective. The thiocyanate is 0.5 g to 5 g and the thioether is 0.2 g to 3 g per mol of silver halide.
Is preferably used. Further, in the present invention, JP-A-61-2
No. 30135 and JP-A-63-25653, a compound which releases an inhibitor during development may be used in combination. Coexist with cadmium salt, zinc salt, lead salt, thallium salt, iridium salt or its complex salt, rhodium salt or its complex salt, iron salt or iron complex salt in the process of silver halide grain formation or physical ripening during the production of silver halide. You may let me. A so-called silver halide solvent such as thiocyanate, thioether compound, thiazolidineethione or tetra-substituted thiourea may be allowed to be present during grain formation. Among them, thiocyanate, 4-substituted thiourea and thioether are preferred solvents for the present invention.

Next, the compound of formula (I), which is a preferred developing agent in the present invention, will be explained in detail. In the general formula (I), preferably R 1 and R 2 are each a hydroxy group, a substituted or unsubstituted amino group (as a substituent, an alkyl group having 1 to 10 carbon atoms, for example, a methyl group, an ethyl group, an n-butyl group, (Including those having a hydroxyethyl group or the like as a substituent), a substituted or unsubstituted acylamino group (acetylamino group, benzoylamino group, etc.), a substituted or unsubstituted alkylsulfonylamino group (methanesulfonylamino group, etc.), Substituted or unsubstituted arylsulfonylamino group (benzenesulfonylamino group, p-toluenesulfonylamino group, etc.), substituted or unsubstituted alkoxycarbonylamino group (methoxycarbonylamino group), mercapto group or substituted or unsubstituted alkylthio group (Methylthio group, ethylthio group, etc.) is represented. Preferred examples of R1 and R2 include a hydroxy group, an amino group, an alkylsulfonylamino group and an arylsulfonylamino group.

P and Q are a hydroxy group, a carboxyl group,
A substituted or unsubstituted alkoxy group, a substituted or unsubstituted hydroxyalkyl group, a substituted or unsubstituted carboxyalkyl group, a sulfo group, a substituted or unsubstituted sulfoalkyl group,
It represents a substituted or unsubstituted amino group, an aminoalkyl group, a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group, or P and Q are bonded to each other to form R ₁ , R ₂
Represents a group of atoms forming a 5- to 8-membered ring with the two vinyl carbon atoms substituted by and the carbon atom substituted by Y. Specific examples of the ring structure _{-O -, - C (R 9} )
_{(R 10) -, - C} (R 11) =, - C (= O) -, - N
(R ₁₂ ) −, −N =, etc. are combined. However, R ₉ , R ₁₀ , R ₁₁ , and R ₁₂ are hydrogen atoms and have 1 to 1 carbon atoms.
0 represents an alkyl group which may be substituted (a hydroxy group, a carboxy group, a sulfo group and the like can be mentioned as the substituent), a hydroxy group and a carboxy group. Further, a saturated or unsaturated condensed ring may be formed on the 5- to 8-membered ring.

Examples of the 5- to 8-membered ring include dihydrofuranone ring, dihydropyrroline ring, pyranone ring, cyclopentenone ring, cyclohexenone ring, pyrrolinone ring, pyrazolinone ring, pyridone ring, azacyclohexenone ring and uracil ring. Examples of preferred 5- to 8-membered rings include a dihydrofuranone ring, a cyclopentenone ring, a cyclohexenone ring, a pyrazolinone ring, an azacyclohexenone ring, and a uracil ring.

Y represents = O or = N-R3. R3
Is a hydrogen atom, a hydroxyl group, a substituted or unsubstituted alkyl group (eg, methyl group, ethyl group, etc.), a substituted or unsubstituted acyl group (eg, acetyl group), a substituted or unsubstituted hydroxyalkyl group (hydroxymethyl group) , A hydroxyethyl group, etc.), a substituted or unsubstituted sulfoalkyl group (sulfomethyl group, sulfoethyl group, etc.), and a substituted or unsubstituted carboxyalkyl group (carboxymethyl group, carboxyethyl group, etc.). Specific examples of the general formula (I) of the present invention are shown below, but the present invention is not limited thereto.

[0034]

[Chemical 10]

[0035]

[Chemical 11]

[0036]

[Chemical 12]

[0037]

[Chemical 13]

[0038]

[Chemical 14]

[0039]

[Chemical 15]

Of these, ascorbic acid or erythorbic acid (diastereomer of ascorbic acid) represented by I-1 and alkali metal salts such as lithium salt, sodium salt and potassium salt thereof are preferable. The developing agent is usually preferably used in an amount of 0.01 mol / liter to 0.8 mol / liter, and particularly preferably used in an amount of 0.05 mol / liter to 0.4 mol / liter. In particular, it is desirable to use a super-additive auxiliary developing agent together with the developing agent represented by the general formula (I).

The auxiliary developing agent exhibiting superadditivity is 1-
Phenyl-3-pyrazolidones auxiliary developing agent or p
-Aminophenols are auxiliary developing agents. 1-Phenyl-3-pyrazolidones as auxiliary developing agents, 1-phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3- Pyrazolidone, 1-phenyl-4,4-dihydroxymethyl-3-pyrazolidone, 1-phenyl-5-methyl-3-pyrazolidone, 1
-P-aminophenyl-4,4-dimethyl-3-pyrazolidone, 1-p-tolyl-4,4-dimethyl-3-pyrazolidone, 1-p-tolyl-4-methyl-4-hydroxymethyl-3-pyrazolidone and so on. Of these, 1-phenyl-4-methyl-4-hydroxymethyl-3
-Pyrazolidone is preferred.

As p-aminophenols auxiliary developing agents, N-methyl-p-aminophenol and N- (β
-Hydroxyethyl) -p-aminophenol, N-
(4-hydroxyphenyl) -glycine, 2-methyl-
Although there are p-aminophenol, p-benzylaminophenol and the like, N-methyl-p-aminophenol is preferable among them.

In the present invention, when the 1-phenyl-3-pyrazolidones or p-aminophenols are used in combination with the auxiliary developing agent together with the developing agent represented by the general formula (I), the former is 0. 01 mol /
L-0.5 mol / l, the latter is preferably used in an amount of 0.001 mol / l-0.1 mol / l, and the latter is preferably used in an amount of 0.005 mol / l-
It is preferably used in an amount of 0.05 mol / l.

The developer used for processing the light-sensitive material of the present invention may contain an amino compound for promoting development.
In particular, JP-A-56-106244 and JP-A-61-267
The amino compounds described in JP-A No. 759 and JP-A No. 2-208652 may be used. The pH of the developer used for processing the light-sensitive material of the present invention is 8.0 to 13.0, preferably 8.3 to 12, and more preferably 8.5 to 10.
It is 5.

The developer preferably used in the present invention contains a carbonate (eg, sodium carbonate, potassium carbonate, etc.) as a pH buffering agent for setting a pH value. The amount of carbonate added is preferably 0.3 mol / liter or more,
Particularly, 0.4 mol / liter or more and 2 mol / liter or less are preferable, and further 0.4 mol / liter or more and 1 mol / liter.
Most preferred is liter or less. The alkaline agent used for setting the pH of the developer used when processing the light-sensitive material of the present invention includes, in addition to the above-mentioned carbonate, a usual water-soluble inorganic alkali metal salt (for example, sodium hydroxide, potassium hydroxide). Etc.) can also be used together. Specifically, in addition to this, a pH buffering agent such as dibasic sodium phosphate, dibasic potassium phosphate, sodium monophosphate, and potassium monophosphate is used, and in addition, the pH buffering agent described in JP-A-60-93433 is used. be able to.

When processing the light-sensitive material of the present invention, the developing solution is used as a silver stain preventing agent for the purpose of Japanese Patent Publication Nos. 62-4702, 62-4703, 63-24123, and 63-24123. The compounds described in Japanese Patent Application No. 3-94955, Japanese Patent Application No. 3-112275 and Japanese Patent Application No. 3-233718 can be used.

The developer used for processing the light-sensitive material of the present invention contains, in addition to the above-mentioned amino compounds, additives such as alkali agents and silver stain inhibitors, developing agents such as potassium bromide and potassium iodide. Inhibitors, organic solvents such as dimethylformamide, methylcellosolve, ethylene glycol, ethanol, methanol, such as 5-methylbenztriazole, 5-chlorobenztriazole, 5-bromobenztriazole, 5-butylbenztriazole, benztriazole, etc. An antifoggant may be added.

Examples of the preservatives of sulfite used in the developing solution for processing the light-sensitive material of the present invention include sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite and potassium metabisulfite. It is preferable to use the sulfite in an amount of 0.01 mol / liter or more, particularly 0.02 mol / liter or more and 2.5 mol / liter or less. In addition, LFA Mason's "Photographic Processing Chemistry" published by Focal Press (1966), pages 226 to 229, U.S. Pat. Nos. 2,193,015 and 2,592,364,
Those described in JP-A-48-64933 may be used.

Further, if necessary, a toning agent, a surface active agent, a water softener, a hardener and the like may be contained. As the chelating agent in the developing solution, ethylenediaminedioltohydroxyphenylacetic acid, diaminopropanetetraacetic acid, nitrilotriacetic acid, hydroxyethylethylenediaminetriacetic acid, dihydroxyethylglycine, ethylenediaminediacetic acid, ethylenediaminedipropionic acid, iminodiacetic acid, diethylenetriaminepentaacetic acid. Acetic acid, hydroxyethyliminodiacetic acid,
1,3-diaminopropanoltetraacetic acid, triethylenetetraminehexaacetic acid, transcyclohexanediaminetetraacetic acid, ethylenediaminetetraacetic acid, glycoletherdiaminetetraacetic acid, ethylenediaminetetrakismethylenephosphonic acid, diethylenetriaminepentamethylenephosphonic acid, nitrilotrimethylenephosphonic acid, 1- Hydroxyethylidene-1,1-diphosphonic acid, 1,1-diphosphonoethane-2-carboxylic acid, 2-phosphonobutane-1,
2,4-tricarboxylic acid, 1-hydroxy-1-phosphonopropane-1,3,3-tricarboxylic acid, catechol-3,4-disulfonic acid, sodium pyrophosphate, sodium tetrapolyphosphate, sodium hexametaphosphate and the like can be mentioned. However, particularly preferably diethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid, 1,3-diaminopropanoltetraacetic acid, glycol etherdiaminetetraacetic acid, hydroxyethylethylenediaminetriacetic acid,
2-phosphonobutane-1,2,4-tricarboxylic acid,
1,1-diphosphonoethane-2-carboxylic acid, nitrilotrimethylenephosphonic acid, ethylenediaminetetrakismethylenephosphonic acid, diethylenetriaminepentaphosphonic acid, 1-hydroxypropylidene-1,1-diphosphonic acid, 1-aminoethylidene-1,1-diphosphonone Acid, 1-hydroxyethylidene-1,1-diphosphonic acid and salts thereof.

In the processing method of the present invention, the replenishing amount of the developing solution is 25 ml or more and 200 ml or less, preferably 30 ml or more and 180 ml or less, and more preferably 60 ml or more and 150 ml or less per 1 m ² of the light-sensitive material.

In the method of processing the light-sensitive material of the present invention, the development processing time is preferably 5 seconds or more and 60 seconds or less. Most preferably, it is 5 seconds or more and 30 seconds or less.

Non-eluting derivatives preferably used in the present invention
Described below are electronic substances. The non-dissolution property of the present invention is
Substantially no elution when the optical material is processed by an automatic processor
The amount of elution is 0 to 1 relative to the amount added.
This is the case of weight%. Conductivity preferably used in the present invention
As the crystalline substance, crystalline metal oxide particles can be used.
For those containing elementary defects and the metal oxide used,
Generally speaking, those containing small amounts of heteroatoms that form
Is particularly preferable because it has high conductivity.
It is particularly preferable because it does not cause fog in the silver halide emulsion. metal
ZnO as an example of oxide, Ti doped with impurities
O₂, SnO₂, Al₂O₃, In ₂O₃, SiO₂,
MgO, BaO, MoO₃, V₂O_FiveEtc. or this
The above composite oxides are preferable, especially ZnO, doped with impurities
TiO₂And SnO₂Is preferred. Examples containing heteroatoms
For example, for ZnO, addition of Al, In, etc.
Addition, SnO₂For Sb, Nb, P, halogen elements
Etc., also TiO₂For Nb, Ta, etc. added
Is effective. The addition amount of these heteroatoms is 0.01
% To 30 mol% is preferable, but 0.1 mol% to
It is particularly preferable if it is 10 mol%. Furthermore, fine particle dispersion
To improve the transparency and transparency
May be added. Conductive material preferred in the present invention
The metal oxide fine particles that are
Product resistivity is 10⁷Ω / cm or less, especially 10^FiveΩ / cm or less
Below. Regarding these oxides, JP-A-56-14
3431, 56-120519, 58-626.
No. 47 and the like.

Further, as described in JP-B-59-6235, a conductive material in which the above metal oxide is attached to other crystalline metal oxide particles or fibrous material (for example, titanium oxide) is used. May be. The particle size that can be used is preferably 1 μm or less, but when it is 0.5 μm or less, stability after dispersion is good and it is easy to use. Further, in order to make the light scattering property as small as possible, it is very preferable to use conductive particles of 0.3 μm or less because a transparent photosensitive material can be formed. There is no particular lower limit of particle size, but 0.01 μm
The above is preferable because the conductivity is improved. When the fine metal oxide particles are needle-like or fibrous, the length is preferably 30 μm or less and the diameter is 1 μm or less, and particularly preferably the length is 10 μm or less and the diameter is 0.3 μm or less. The ratio is 3 or more. These conductive metal oxides which are preferable in the present invention may be coated from a coating liquid without a binder, and in that case, it is preferable to further coat a binder thereon.

The metal oxide preferably used in the present invention is more preferably coated with a binder. The binder is not particularly limited, but may be, for example, a water-soluble binder such as gelatin, dextran, polyacrylamide, starch, polyvinyl alcohol, poly (meth) acrylic acid ester, polyvinyl acetate, polyurethane, polyvinyl chloride, Synthetic polymer binders such as polyvinylidene chloride, styrene / butadiene copolymer, polystyrene, polyester, polyethylene, polyethylene oxide, polypropylene, polycarbonate may be used in the organic solvent, and these polymer binders may be used in the form of aqueous dispersion. May be used in. Further, these metal oxides may be used as a mixture of spherical and fibrous ones. The content of the metal oxide preferably used in the present invention is 0.0005 g /
m ² or more and 1.0 g / m ² or less, more preferably 0.0
010 to 0.5 g / m ² , particularly preferably 0.0050 to
It is 0.3 g / m ² .

Further, a heat-resistant agent in a layer comprising a metal oxide, which is preferable in the present invention, within a range not impairing the effects of the present invention,
A weathering agent, inorganic particles, a water-soluble resin, an emulsion and the like may be added for matting and improving the film quality. For example, inorganic fine particles may be added to the layer composed of the metal oxide preferable in the present invention. Examples of the inorganic fine particles to be added include silica, colloidal silica, alumina, alumina sol, kaolin, talc, mica, calcium carbonate and the like. The fine particles have an average particle size of 0.01 to 10
μm is preferable, more preferably 0.01 to 5 μm, and the weight ratio is preferably 0.05 to 10 parts, and particularly preferably 0.1 to 5 parts with respect to the solid content in the coating agent. Further, various organic or inorganic curing agents may be added to the coating composition of the present invention. These curing agents may be low molecular weight compounds or high molecular weight compounds, and these may be used alone or in combination.

As the low molecular weight curing agent, for example, tea
"The Theory of the Photographic Process" by TH James
ory of the Photographic Process) ”, 4th edition, pp. 77-88, low molecular weight curing agents are used, among which those having vinyl sulfonic acid, aziridine group, epoxy group, triazine ring are preferable, The low molecular weight compounds described in JP-A-53-41221 and JP-A-60-225143 are preferable. The polymeric curing agent preferably has at least two groups in the same molecule that oppose to hydrophilic colloids such as gelatin, and has a molecular weight of 2
Examples of the group that is a compound of 000 or more and that reacts with a hydrophilic colloid such as gelatin include, for example, aldehyde groups, epoxy groups, active halides (dichlorotriazine, chloromethylstyryl groups, chloroethylsulfonyl groups, etc.), active vinyl groups, Examples thereof include active ester groups.

Examples of the polymeric curing agent used in the present invention include dialdehyde starch, polyacrolein, polymers having an aldehyde group such as acrolein copolymers described in US Pat. No. 3,396,029, US Pat. Polymers having epoxy groups described in 3,623,878, Research Disclosure 17333 (1)
978), polymers having a dichlorotriazine group, polymers having an active ester group described in JP-A-56-66841, JP-A-56-1.
Nos. 4,252,4, U.S. Pat. No. 4,161,407, JP-A-54-65033, Research Disclosure Magazine 16725 (1978), and the like, are polymers having an active vinyl group or a group serving as a precursor thereof. It is particularly preferred that the active vinyl group or a group which is a precursor thereof is bonded to the polymer main chain by a long spacer as described in JP-A-56-142524.

Next, the conductive polymer or latex preferably used in the present invention will be described. The conductive polymer used is not particularly limited and may be any of anionic, cationic, betaine and nonionic, and among them, anionic and cationic are preferable.
More preferred are anionic sulfonic acid-based, carboxylic acid-based, and phosphoric acid-based polymers or latexes, and tertiary amine-based, quaternary ammonium-based, and phosphonium-based polymers. These conductive polymers are disclosed, for example, in Japanese Examined Patent Publication No. 52
-25251, JP-A-51-29923, JP-B-6
0-48024 anionic polymer or latex, JP-B-57-18176, 57-56059
Nos. 58-56856, US Pat. No. 4,118,231 and the like, and cationic polymers or latexes can be mentioned. Specific examples of these conductive polymers or latices will be described below, but the present invention is not limited thereto.

[0059]

[Chemical 16]

[0060]

[Chemical 17]

In the present invention, a metal oxide is most preferably used as the conductive substance in that the non-elution property into the treatment liquid is good. The addition layer of the conductive metal oxide, polymer and latex preferably used in the present invention is not particularly limited as long as it is the side having the emulsion on the support, and examples thereof include a protective layer, an intermediate layer, an emulsion layer and a UV layer. , An antihalation layer and an undercoat layer. Among these, a protective layer, an intermediate layer, an antihalation layer and an undercoat layer are preferable, and an undercoat layer, an intermediate layer and an antihalation layer are particularly preferable.

Various additives and the like used in the photographic light-sensitive material of the present invention are not particularly limited, and for example, the ones described in the following relevant parts can be used. Item This section 1) Silver halide emulsion and JP-A-2-68539, page 8, lower right column, bottom 6 from its manufacturing line to page 10, upper right column, line 12, and 3-245 37 Gazette, page 2, lower right column, line 10 to page 6, upper right column, line 1; page 10, upper left column, line 16 to page 11, lower left column, line 19. 2) Chemical sensitization method JP-A-2-68539, page 10, upper right column, line 13 to upper left column, line 16 3) Antifoggants and Stabilizers JP-A-2-68539, page 10, lower left column, line 17 to page 11, upper left column, line 7 and page 3, lower left column, line 2 to page 4, lower left column . 4) Color tone improving agent JP-A-62-276539, page 2, lower left column, line 7 to page 10, left lower column, line 20; JP-A-3-94 249, page 6, lower left column, line 15 to Page 11, right upper column, line 19 5) Spectral sensitizing dye JP-A-2-68539, page 4, lower right column, line 4 to page 8, lower right column. 6) Surfactant JP-A-2-68539, page 11, upper left column, line 14 Antistatic agent to page 12, upper left column, line 9 7) Matting agent, slipping agent JP-A-2-68539, page 12, upper left column, line 10 Plasticizer, same as upper right column, line 10; page 14, lower left column, line 10 to lower right column, line 1

[0063] 8) Hydrophilic colloid JP-A-2-68539, page 12, upper right column, line 11                           From the eye, the lower left column, 16th line. 9) Hardener JP-A-2-68539, page 12, lower left column, line 17                           From the same page, page 13, upper right column, line 6 10) Support, JP-A-2-68539, page 13, upper right column, line 7                           From the 20th line. 11) Crossover JP-A-2-264944, page 4, upper right column, line 20     From the cut method, page 14, upper right column. 12) Dyes and mordants JP-A-2-68539, page 13, lower left column, line 1                           To page 14, lower left column, line 9 of the same. No. 3-24537                           Gazette, page 14, lower left column to page 16, lower right column. 13) Polyhydroxy Same as from the upper left column on page 11 of JP-A-3-39948     Benzene, page 12, lower left column, EP Patent No. 452772A                           . 14) Layer structure JP-A-3-198041. 15) Development processing method JP-A-2-103037, page 16, upper right column, line 7                           From the eye, page 19, lower left column, line 15, and JP-A-2-                           No. 115837, page 3, lower right column, line 5 to line 6                           Top right column, line 10

[0064]

【Example】

Example 1 (Preparation of emulsion T1) 5.0 g of ammonium nitrate, 6.9 g of potassium bromide and 3.5 g of low molecular weight gelatin having an average molecular weight of 15,000 were added to 1 liter of water, and the mixture was kept at 50 ° C. While stirring, 40 ml of silver nitrate aqueous solution (silver nitrate 4.0
35 ml of an aqueous solution containing g) and 0.85 g of potassium bromide was added by the double jet method in 40 seconds. Then 6
Aqueous silver nitrate solution (4.0g of silver nitrate)
40 ml was added over 10 minutes, and potassium bromide 1.0 was added.
g and 18.4 g of gelatin were added.

Next, 15 ml of 1N caustic soda was added and physically aged for 20 minutes at 60 ° C., and then 4 ml of 100% acetic acid was added. Subsequently, an aqueous solution of 162 g of silver nitrate and an aqueous solution of potassium bromide were added over 35 minutes while maintaining the pAg at 8.6 and adding a flow rate by the control double jet method. Next, 35 ml of 2N potassium thiocyanate solution was added, and after 5 minutes, the temperature was lowered to 35 ° C. The obtained silver halide grains are pure silver bromide tabular grains in which the total projected area of tabular grains having an aspect ratio of 3 or more and 30 or less accounts for 96% of the total projected area of all grains. The average circle-equivalent diameter of the projected area was 0.7 μm, the average thickness was 0.12 μm, the variation coefficient of diameter was 25%, and the average aspect ratio of each grain was 6.7.

After that, soluble salts were removed by the coagulation sedimentation method. The temperature was raised to 40 ° C. again, and 35 g of gelatin, 0.1 g of phenoxyethanol and 0.4 g of sodium polystyrene sulfonate as a thickener were added, and the pH was adjusted to 6.4 and pAg 8.2 with caustic soda and an aqueous silver nitrate solution.

This emulsion was chemically sensitized while being kept at 56 ° C. with stirring. To an emulsion of 1 mol of silver halide, 0.33 g of potassium iodide was added, and then 0.2 g of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added, 3.5 mg of sodium ethylthiosulfinate was added. 1 of compound A-1
× 10 ⁻³ mol, 4 × 1 of compound A-2 as a supersensitizer
They were added successively to 0 ^-6 mole. Further, 4.6 mg of chloroauric acid and 60 mg of potassium thiocyanate were added. Subsequent sensitization with a chalcogen compound was carried out in the following two ways. (See chalcogen sensitization column in Table 1)

"Se-type sensitization method" Sodium thiosulfate was added to 5
× 10 ^-6 mol and 6.5 × 10 ^-6 mol of the selenium compound A-3 were added. “S-type sensitization method” 15 × 10 ⁻⁶ mol of sodium thiosulfate was added. In both cases, after 20 minutes, add 6 × 10 sodium sulfite.
^-4 mol was added, and after 40 minutes, 20 mg of compound A-4 was added.
Add and cool to 35 ° C. Thus tabular grain emulsion T
1 was prepared.

[0069]

[Chemical 18]

(Preparation of emulsion C1) A pure silver bromide cubic emulsion was prepared with the same silver amount as emulsion T1. The average circle-equivalent diameter of the projected area of the grain was 0.6 micron, and the variation coefficient of the diameter was 20%. The coagulation-precipitation method and the dispersion method were performed in the same manner as in T1, and the chemical sensitization was also performed under the same conditions as in T1. (Se type sensitization method)

(Preparation of Emulsion Layer Coating Solution) An emulsion layer coating solution was prepared so that each component added to the emulsions T1 and C1 had the following coating amount per one side of the support.・ 2,6-Bis (hydroxyamino) -4-diethylamino-1,3,5-triazine 1.7 mg / m ²・ Dextran 0.45 g / m ²・ Sodium polystyrene sulfonate (average molecular weight 600,000) 33 mg / m ² (including emulsion addition) ・ Gelatin 1.1 g / m ² (including emulsion addition) Hardener 1,2-bis (vinylsulfonylacetamide) ethane (with a swelling rate of 250% in Table 1) (Case) (35 mg / m ² ) (when the swelling ratio is 180% in Table 1) (55 mg / m ² ) (when the swelling ratio is 120% in Table 1) (95 mg / m ² ) ・ Compound A-50 .11 g / m ² · Dye Emulsion b (as dye solid content) 4.0 mg / m ² · Dye Emulsion m (as dye solid content) 4.0 mg / m ²

[0072]

[Chemical 19]

(Preparation of Dye Emulsion b)
0 g and 2,4-diamylphenol 62.8 g,
62.8 g of dicyclohexyl phthalate and 333 g of ethyl acetate were dissolved at 60 ° C. Next, 65 ml of a 5% aqueous solution of sodium dodecylbenzenesulfonate, 94 g of gelatin and 581 ml of water were added, and the mixture was mixed with a dissolver to 60
Emulsified and dispersed at 30 ° C. for 30 minutes. Next, 2 g of methyl p-hydroxybenzoate and 6 liters of water were added, and the temperature was lowered to 40 ° C. Next, Asahi Kasei Ultrafiltration Lab Module AC
Using P1050, concentrate until the total amount is 2 kg, p
-Dye emulsion b by adding 1 g of methyl hydroxybenzoate
And

[0074]

[Chemical 20]

(Preparation of Dye Emulsion m) 10 g of Dye-2
Dye emulsion m was prepared by weighing, dissolving in a solvent consisting of 10 ml of tricresyl phosphate and 20 ml of ethyl acetate and then emulsifying and dispersing in 100 ml of 15% gelatin aqueous solution containing 750 mg of anionic surfactant. .

[0076]

[Chemical 21]

(Preparation of Dye Dispersion i) Dye-3 was treated as a wet cake without drying as much as possible, and 15 g of a 5% carboxymethylcellulose aqueous solution was added to 2.5 g of the dry solid content to make a total amount of 63.3 g. As
Mix well to form a slurry. Prepare 100 ml of glass beads having a diameter of 0.8 to 1.2 mm, put this slurry in a disperser (1 / 16G sand grinder mill; manufactured by AIMEX Co., Ltd.) and disperse for 12 hours. Water was added to the mixture so as to obtain a dye dispersion i.

[0078]

[Chemical formula 22]

(Preparation of Surface Protective Layer Coating Solution) A surface protective layer coating solution was prepared so that the components of the surface protective layer had the following coating amounts.・ Gelatin 0.60 g / m ²・ Proxel 1.4 mg / m ²・ Sodium polyacrylate (average molecular weight 410,000) 17 mg / m ²・ Additive-1 35 mg / m ²・ Additive-2 5.4 mg / M ² · Additive-3 22.5 mg / m ² · Additive-4 0.5 mg / m ² · Mat agent-1 (average particle size 3.7 microns) 72.5 mg / m ²

[0080]

[Chemical formula 23]

(Preparation of coating liquid for intermediate layer) Gelatin 0.50 g / m ² Proxel 1.4 mg / m ² Sodium polyacrylate (average molecular weight 41,000) 17 mg / m ² Compound A-6 4 .4mg / m ² · compound A-7 1.3mg / m ² · compound A-8 0.5mg / m ² · dye dispersion i (as dye solid) 18 mg / m ²

[0082]

[Chemical formula 24]

(2) Preparation of Support Corona discharge was performed on a biaxially stretched polyethylene terephthalate film having a thickness of 175 μm, and the first undercoating liquid having the following composition was applied at an amount of 4.9 ml / m ^2. Thus, it was coated with a wire bar coater and dried at 185 ° C. for I minutes. Next, a first undercoat layer was similarly provided on the opposite surface. The polyethylene terephthalate used had a dye-1 content of 0.04% by weight.・ Butadiene-styrene copolymer latex solution (solid content 40% butadiene / styrene weight ratio = 31/69) 158 ml ・ 2,4-dichloro-6-hydroxy-s-triazine sodium salt 4% solution 41 ml ・ Distilled water 801 ml * in latex solution Contains compound A-9 as an emulsifying dispersant in an amount of 0.4% by weight based on the latex solid content.

[0084]

[Chemical 25]

(Preparation of Development Replenisher) A development replenisher A having the following formulation as sodium erythorbate as a developing agent was prepared. Diethylenetriamine pentaacetic acid 8.0 g Sodium sulfite 19.6 g Sodium hydrogen sulfite 2.8 g Sodium carbonate monohydrate 52.0 g Potassium carbonate 55.0 g Sodium erythorbate 60.0 g 4-Hydroxymethyl-4-methyl-1-phenyl- 3-Pyrazolidone 13.2 g 3,3'-diphenyl-3,3'-dithiopropionic acid 1.44 g Diethylene glycol 50.0 g Water is added to make 1 liter. Adjust to pH 10.1 with sodium hydroxide or acetic acid.

(Preparation of developing mother liquor) The above-mentioned developing replenisher A 2
1 liter was diluted with water to 4 liters, and a starter solution having the following composition was added in an amount of 55 ml per 1 liter of development replenisher A.
The developing mother liquor was adjusted to pH 9.5. Starter solution Potassium bromide 11.1 g Acetic acid 10.8 g Water is added to bring the total volume to 55 ml.

(Preparation of Fixing Replenisher) A fixing replenisher having the following formulation was prepared. Water 0.5 liters Ethylenediaminetetraacetic acid dihydrate 0.05g Sodium thiosulfate pentahydrate 300g Sodium bisulfite 98.0g Sodium hydroxide 2.91g Adjust pH to 5.4 with NaOH and add water to 1 liter And

(Preparation of fixing mother liquor) 2 liters of the above fixing replenisher was diluted with water to 4 liters. The pH was 5.6.

(Method of processing photographic material) Aperture ratio of 0.02
Fuji Photo Film Co., Ltd. improved automatic processor F
PM-1300, using the above developer and fixer,
Development replenisher and fixer replenisher 10 per 1 m ² of light-sensitive material
It was processed while supplementing 3 ml. The breakdown of each process when operating in dry to dry 120 seconds is described. Process Temperature Processing time Image 35 ° C 25 seconds Fixing 35 ° C 25 seconds Water washing 25 ° C 30 seconds Dry 55 ° C 40 seconds Total (dry to dry) 120 seconds

(Preparation of Photographic Material) The coating solutions for the emulsion, surface protective layer and intermediate layer prepared above were sequentially coated on both sides of the above-mentioned support under the same conditions by the simultaneous extrusion method. The amount of gelatin in the emulsion layer and the amount of each chemical in the emulsion layer are changed for each coating solution so that the coating amount is constant. The coated silver amount of each photographic material is set so as to be the amount (g / m ² ) shown in Table 1. In addition,
The swelling ratio was measured according to the definition described in the text.

[0091]

[Table 1]

(Evaluation of Photographic Performance) Using the above processing solution and an automatic processor, 1,000 pieces of photographic material 6 having a size of 4 pieces (blackening rate of 40%) were processed according to the above-mentioned replenishing method, and were put into a running state. . Fuji Photo Film Co., Ltd. for each photographic material
An X-ray orthoscreen HG-M manufactured by K.K. was used to expose for 0.1 seconds from both sides, and the processing time was changed from development to drying for 120 seconds (development time 25 seconds). 18
A 0 second treatment (developing time: 38 seconds) was performed to evaluate the sensitivity. The sensitivity obtained by processing the photographic material 1 for 120 seconds is 10
As 0, the photographic sensitivity of each photographic material was represented by the reciprocal of the ratio of the exposure amount given when the development density reached 50% of the maximum density obtained by processing for 180 seconds and that of photographic material 1.
It is preferable that the numerical value indicating the sensitivity is large. The development density was a value obtained by subtracting the fog density of the support and the unexposed area, and the maximum density was the value obtained by subtracting the support density.
In Table 2, Dmax is indicated by ◯ when the development density in the 120-second process is sufficiently saturated at the given maximum exposure amount and is equal to the maximum density in the 180-second process, and is not saturated. In the case, it is indicated by the symbol X. The sample indicated by x indicates that the development was not completed at the development time.

(Evaluation of Drying Property) 3
When each sample of 5 cm × 35 cm (large-angle size) was treated for 120 seconds, the sample coming out of the drying zone outlet was touched and evaluated. ◯: It is well dried. X: Moisture is a problem.

The results are shown in Table 2. The photographic material of the present invention is 1
20 seconds processing gives a sensitivity comparable to 180 seconds processing, Dm
With ax, the development is fully completed in 120 seconds. It is understood that the photographic material of the present invention has high sensitivity and gradation stability and good drying property.

[0095]

[Table 2]

Example 2 Pure silver bromide tabular grains obtained by changing the amount of low molecular weight gelatin to 5.0 g in the method for preparing emulsion T1 of Example 1 were designated as T2. In the obtained silver halide grains, tabular grains having an aspect ratio of 3 or more and 30 or less account for 97% of the total projected area of the grain, and the average value of the equivalent circle diameters of the projected area of the grain is 1.0 micron. The coefficient of variation of was 30%.
The average particle thickness was 0.16 micron.

The coagulation-sedimentation method and the dispersion method were the same as those in T1, and the chemical sensitization was carried out by adding half the amount of each chemical of T1 "Se type sensitization method". The emulsion T2 was used for coating in the same manner as in the photographic materials 4 and 6 of Example 1 to obtain photographic materials 12 and 13. (See Table 3) The swelling rates of the photographic materials 12 and 13 were 180% as in the photographic materials 4 and 6. The processing method and the photographic evaluation method are the same as in Example 1.

The results are shown in Table 3. Photographic material 1 using Emulsion T2 having a grain size larger than T1 and having an average equivalent circle diameter of projected areas of silver halide grains of 1.0 micron.
No. 3 is preferable for the treatment for 180 seconds because of its high sensitivity.
It has the same sensitivity as the photographic material 6 in the second processing. The photographic material 6 is excellent in that the maximum density is high.

[0099]

[Table 3]

Example 3 (Preparation of Support Having Coated Conductive Layer) As the second undercoat layer of the support of Example 1, one side was electrically conductive by the wire bar coater method so that the amount was as described below. The functional layer was applied and dried to prepare a support.・ Gelatin 19 mg / m ²・ SnO ₂ / Sb (9/1 weight ratio, average particle size 0.24 micron) 160 mg / m ²

(Preparation of Photographic Material) On the above prepared support, an emulsion layer, an intermediate layer and a surface protective layer having the same formulation as the coating sample 6 of Example 1 were coated on both sides in the same manner as in Example 1. did. This coated sample was designated as 14. Further, a sample applied by removing the additive 1 from the formulation of the surface protective layer of the coated sample 14 was designated as a coated sample 15.

(Measurement of Surface Resistance Value) Samples 6, 14, 15
Each sample was aged for 6 hours in an environment of 25 ° C. and 10% RH,
The surface resistance value (logSR) was measured. (Method and evaluation of low replenishment processing) Using the automatic processor and the processing solution used in Example 1, starting from a new solution, under the replenishment condition of 5 ml / 4 pieces size, samples 6 and 14,
For each of the 15 samples, 1000 sheets (4 pieces size) exposed so that the development rate was 40% were processed. The processing time was 120 seconds. The evaluation was made by comparing the degree of development unevenness of the processed film with the amount of bubbles in the developer. Regarding the development unevenness, the processed films from the 900th sheet to the 1000th sheet are observed. When the development unevenness is large, it is ×, when the development unevenness is slightly generated, but there is no problem in practical use, Δ, almost no unevenness can be found. The case was ◯. 100 bubbles of developer
Observe the developing tank in the operating state immediately after processing 0 sheets, "Yes" in Table 4 when there is bubbles on the roller, "No" when bubbles can hardly be found
Described as.

As shown in Table 4, the coated sample 15 having a conductive layer has excellent electrostatic characteristics even in an extremely low replenishment treatment such as in this experiment, and has preferable characteristics in which bubbles and development unevenness hardly occur. I understand.

[0104]

[Table 4]

The coated samples 14 and 15 both have a swelling ratio of 175.
%, And the drying property was as good as that of Sample 6. Further, in both 120-second processing and 180-second processing, the photographic performance such as sensitivity and Dmax was equivalent to that of Sample 6.

Example 4 (Preparation of Emulsion A for the Present Invention) Silver chloride tabular grains were prepared as follows.

[0107]

[Chemical formula 26]

Solution (2) and solution (3) were simultaneously added to solution (1) kept at 35 ° C. with stirring over 1 minute, and the temperature of the solution was raised to 50 ° C. over 15 minutes. At this point, grains corresponding to about 5.7% of total silver were formed. Then add solution (4) and solution (5) simultaneously over 24 minutes,
Further, the solution (6) and the solution (7) were simultaneously added over 40 minutes to obtain a tabular silver chloride emulsion A. The emulsion was washed with water and desalted by the precipitation method, 30 g of gelatin and H ₂ O were added, 2.0 g of phenoxyethanol and 0.8 g of sodium polystyrene sulfonate as a thickener were added, and the pH was adjusted to 6.0 with caustic soda. Redistributed. The obtained silver halide grains had an average circle-equivalent diameter of the projected area of the grain of 0.68 μm, an average grain thickness of 0.11 μm, a variation coefficient of the circle-equivalent diameter of 19%, and an average aspect ratio of 6.5. Is a tabular grain of silver chloride having the (1.1.1) plane as the main plane. The sum of the projected areas of tabular grains having an aspect ratio of 3 or more and 30 or less occupied 95% of the projected area of all grains.

The chemical sensitization of this emulsion was carried out under the same conditions as in T1 of Example 1. (Implemented by Se type sensitization method)

(Preparation of emulsion B for the present invention) 1200 ml of an aqueous gelatin solution (containing 18 g of deionized alkali-treated bone gelatin having a methionine content of about 40 μmol / g, pH 4.3) was placed in a reaction vessel, and the temperature was 35 ° C. Keeping A
Solution g-1 (including 20 g of AgNO _{3 in} 100 ml, 0.8 g of the gelatin and 0.2 ml of HNO ₃ 1N solution) and solution X-1 (6.9 g of NaCl in 100 ml, 0.8 of the gelatin)
g, including 0.3 ml of NaOH 1N solution) at 24 ml / min.
Only 2 ml was added at the same time. After stirring for 2 minutes, Ag-
Solution 2 (2 g of AgNO ₃ in 100 ml of gelatin, 0.
8g, including HNO ₃ 1N solution 0.2ml) and X-2 solution (1
1.4 g of KBr in 0.8 ml, 0.8 g of the gelatin, N
AOH 1N solution (containing 0.2 ml) was simultaneously mixed and added at 19 ml / min at a rate of 31 ml. After stirring for 2 minutes, Ag-1 solution and X-1 solution were simultaneously mixed and added at 48 ml / min in an amount of 36 ml.
20 ml of NaCl-1 solution (containing 10 g of NaCl in 100 ml) was added to adjust the pH to 4.8 and the temperature was raised to 60 ° C. After aging for 20 minutes, lower the temperature to 60 ° C,
After adjusting the pH to 5.0, Ag-3 solution (containing 10 g of AgNO _{3 in} 100 ml) and X-3 solution (containing 100 g of NaCl in 100 ml) were added to CDJ at a silver potential of 130 mV.
(controlled double jet) was added. The flow rate at the start of addition was 7 ml / min, and the flow rate was accelerated at 0.1 ml / min per minute, and 400 ml of Ag-3 solution was added.

A precipitating agent was added, the temperature was lowered to 30 ° C., the mixture was washed with settling water, an aqueous gelatin solution was added, and the pH was adjusted to 6.
2, adjusted to pCl 3.0. A part of the emulsion was sampled, and a transmission electron micrograph image (hereinafter referred to as "TEM image") of the grain replica was observed. The grains were tabular grains having (1.0.0) as the main plane, and the shape characteristic values were as follows. (Aspect ratio of 3 to 30 (10
0) total projected area of tabular grains / sum of projected areas of all AgX grains) is 0.94, and average aspect ratio (average diameter / average thickness) of (100) tabular grains having an aspect ratio of 2 or more is 8. 2. The average circle equivalent diameter of the projected area of particles is 0.71μ
m, (total projected area of twin grains / total projected area of (100) tabular grains having an aspect ratio of 2 or more) = 0, ((100) tabular grains having an aspect ratio of 2 or more and an edge ratio of 1 to 1.4 Total projected area / total projected area of all AgX particles) =
0.86, (coefficient of variation in diameter distribution of (100) tabular grains having an aspect ratio of 2 or more when 70% of the total projected area is taken out from the larger one) = 0.059, and the average thickness is It was 0.10 μm.

With respect to this silver halide emulsion, the coagulation sedimentation method, the dispersion method and the chemical sensitization method were carried out under the same conditions as those for the emulsion A.

(Preparation of Coating Sample) Each of the above emulsions A and B was coated on both sides of the support in the same formulation as in Sample 15 of Example 3. Sample 16 coated with Emulsion A,
Sample 17 was prepared by coating emulsion B. Samples 16, 1
7, the coated silver amount on one side was 1.4 g / m ² , and the swelling rate was 175.
%Met.

The coated samples 16 and 17 of the present invention are the same as the sample 6 of the example 1 in the processing method of the example 1.
The drying property in 0 second treatment was good, and the sensitivity and Dmax were also good results in 120 second treatment.

[0115]

According to the present invention, it is possible to provide a light-sensitive material satisfying high sensitivity, Dmax and dryness even in short-time development.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ identification code FI G03C 5/29 G03C 5/29 5/31 5/31 (58) Fields investigated (Int.Cl. ⁷ , DB name) G03C 1 / 035 G03C 1/09 G03C 1/30 G03C 1/74 G03C 1/85 G03C 5/29 G03C 5/31

Claims (3)

(57) [Claims] 1. A photographic light-sensitive material in which at least one side of a support is coated with at least one light-sensitive silver halide emulsion layer, wherein at least one side of the support comprises:
The coated silver amount is 0.5 g / m ² or more and 1.5 g / m ² or less,
Projected area of silver halide grains contained in the emulsion layer
50% or more and 100% or less has an aspect ratio of 3 or more and 30 or less
The lower tabular silver halide grain is a photosensitive halogenated
The average value of the equivalent circle diameter of the projected area of silver particles is 0.1 micron
And 0.8 μm or less, and the photosensitive silver halide grains in the emulsion layer are sensitized with a selenium compound, and the swelling ratio of the total hydrophilic colloid layer on the emulsion layer side of the photographic light-sensitive material is 130. der Ru halogen than 200% more than%
The silver halide photographic light-sensitive material was processed with an automatic processor to obtain the compound represented by the general formula (I)
Containing a developing agent represented by
Development time of 5 seconds or less with a developer that does not contain benzene compounds
Halogen characterized by being developed in less than 30 seconds
Processing method of silver halide photographic light-sensitive material. [Chemical 1] In the formula, R1 and R2 are a hydroxyl group and an amino, respectively.
Represents a group, a mercapto group, or an alkylthio group. P,
Q is hydroxyl group, carboxyl group, alcohol
Xy, hydroxyalkyl, carboxyalkyl
Group, sulfo group, sulfoalkyl group, amino group, alkyl
A group, or an aryl group, or P and Q are
Two vinyl carbons bound to R1 and R2 substituted
A 5- to 8-membered ring together with the carbon atom substituted by the atom and Y
Represents a group of atoms to be formed. Y is = O, or = N-R3
Represent R3 is a hydrogen atom, a hydroxyl group, an alkyl group,
Acyl group, sulfoalkyl group or carboxyalkyl
Represents a group. 2. A silver halide photographic light-sensitive material having a layer containing a non-eluting conductive substance.
A method of processing a silver halide photographic light-sensitive material according to claim 1.
Law. 3. The replenishing amount of the developer is 25 ml or more and 200 ml or less per 1 m ^{2 of the} light-sensitive material.
The method for processing a silver halide photographic light-sensitive material as described in 1 or 2 .