JPH07199389A - Rapidly processable silver halide photographic sensitive material high in sensitivity - Google Patents

Abstract

PURPOSE:To provide the silver halide photographic sensitive material capable of rapid processing and freed of fluctuation of fog and sensitivity due to change of processing process and stable in photographic performance and high in sensitivity. CONSTITUTION:The photosensitive material contains in its photosensitive silver halide emulsion layer silver iodobromide or chlorobromide grains satisfying the following conditions in an amount of >=30% of the projection areas of the total silver halide grains in the same layer: (I) The silver halide grains have an average grain diameter of <=0.5mum; (2) an amount of a thiocyanic acid compound present on the surfaces of the grains is 1.0X10<-3>-4.0X10<-2>mol; and (3) Vcore/Vtotal <0.3, where Vgore and Vtotal are the volume of a core and Vtotal is the total grain.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a high-sensitivity silver halide photographic light-sensitive material capable of rapid processing, and more specifically, a silver halide photographic having stable photographic performance with less fog and sensitivity variation due to different processing steps. It relates to a photosensitive material.

[0002]

2. Description of the Related Art In recent years, in the field of silver halide photographic light-sensitive materials, rapid processing at high temperature has been rapidly spread. Therefore, it is essential to develop a silver halide photographic light-sensitive material excellent in development progress and processability. For such a purpose, it is generally known to reduce the silver iodide content of silver halide grains or reduce the amount of coated silver to accelerate the development progress.

In recent years, it has been possible to improve developability and covering power by using tabular grains, for example, US Pat. No. 4,434,
Many are disclosed such as No. 226 and No. 4,413,053. Furthermore, it is disclosed, for example, in JP-A-63-305343 or JP-A-1-770474 that the developability can be improved by controlling the development start point of silver halide grains having a (111) plane.

However, although each of these techniques has its own characteristics, it is not suitable for a silver halide photographic light-sensitive material having a relatively small silver halide grain size and high sensitivity, and has a rapid processing property. Was not enough.

In the present invention, thiocyanate is present on the surface of silver halide grains to give a relatively small grain size, high sensitivity and rapid processability.

Regarding the thiocyanic acid compound, for example, US Pat. Nos. 2,222,256 and 3,320,069, and JP-A-62-185383.
It is disclosed in the publication No., etc. that it can be present at the time of silver halide grain formation to obtain high sensitivity. However, according to the study by the present inventor, the effect of thiocyanic acid under these conditions is not sufficient until the development speed is sufficiently improved. It didn't reach.

[0007]

Therefore, the object of the present invention is to enable rapid processing and to prevent fogging due to the difference in processing steps.
(EN) A high-sensitivity silver halide photographic light-sensitive material having stable photographic performance without variation in sensitivity.

[0008]

The objects of the present invention have been achieved by the following.

That is, on at least one side of the support,
A silver halide photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer, the silver halide emulsion layer satisfying the following conditions (1), (2) and (3): Alternatively, a silver halide photographic light-sensitive material characterized by containing silver chloroiodobromide grains in an amount of at least 30% of the total projected area of silver halide grains present in the same layer.

(1) The average grain size of silver halide grains is 0.5 μm
(2) The amount of thiocyanic acid compound present on the surface of silver halide grains is 1.0 × 10 ⁻³ mol or more and less than 4.0 × 10 ⁻² mol per mol of silver (3) Vcore / Vtotal <0.3 (However, Vcore in the formula represents the volume of the silver halide grains of the core, and Vtotal represents the volume of the silver halide grains in the final grain size.) The present invention will be described in detail below.

The term "core" as used in the present invention means the inner layered portion of the silver halide grain having a definite layered structure,
The outer layered portion is called a shell.

The definite layered structure referred to herein can be determined by an X-ray diffraction method. An example of application of X-ray diffraction to silver halide grains is described in H. Hirsch, Journal of Photographic Science, Vol. 10 (1962), p. 129 et seq.

When the lattice constant is determined by the halogen composition, a diffraction peak occurs at a diffraction angle satisfying the black condition (2dsin θ = nλ). X-ray diffraction can be measured by, for example, Basic Analytical Chemistry Course 24 “X-ray analysis” (Kyoritsu Publishing) or “X-ray analysis”.
Line Diffraction Guide ”(Rigaku Denki Co., Ltd.) and the like. As a standard measurement method, Cu was used as a target and Cu Kβ ray was used as a radiation source (tube voltage 40 kv, tube current 60 m
A) This is a method of obtaining the diffraction curve of the (220) plane of a silver halide grain.

In order to increase the resolution of the measuring instrument, the width of the slit (divergence slit, light receiving slit, etc.) of the measuring instrument, the time constant of the device, the operating speed of the goniometer, the recording speed, etc. are properly selected, and a standard sample such as silicon is selected. Use to confirm accuracy.

When the silver halide grain has two distinct layered structures, the diffraction maximum due to silver halide in the high iodine layer and the diffraction maximum in the low iodine layer appear, and two peaks appear in the diffraction curve.

In the present invention, two distinct layered structures mean that the diffraction intensity (diffraction angle) of the (220) plane of silver halide is determined by using the Kβ line of Cu in the diffraction angle (2θ) range of 38 to 42 °. When a curve is obtained, two diffraction peaks corresponding to the high iodine layer containing 10 to 45 mol% of silver iodide and one minimum appear between them, and the curve corresponds to the high iodine layer. The diffraction intensity is 1/10 to the diffraction intensity of the peak corresponding to the low iodine layer.
Say when it is 3/1. More preferably, the diffraction intensity ratio is 1/5 to 3/1.

In the emulsion having a clear layered structure, the minimum value of the diffraction intensity between the two peaks is preferably 90% or less of the two diffraction maximums (peaks) having weaker intensity, and more preferably. 80% or less, more preferably
It is less than 60%. Means for resolving a diffraction curve composed of two diffraction components are well known, and are described, for example, in Experimental Physics Course 11 Lattice Defects (Kyoritsu Shuppan).
It is also useful to assume that the curve is a function such as a Gaussian function or a Lorentz function and to analyze it using a curve analyzer manufactured by Du Pont.

As the thiocyanic acid compound used in the present invention, a water-soluble salt such as a metal thiocyanate or NH ₄ SCN can be used. In the case of a metal salt, a metal element which does not adversely affect the photographic performance, for example, NH ₄ SCN, KSCN and NaSC
It is preferable to use N or the like. Further, a sparingly soluble salt such as AgSCN may be added in the form of fine particles, and in that case, the size is preferably 0.2 μm or less, and more preferably 0.05 μm or less.

The thiocyanic acid compound may be added at any time during the emulsion production process, but it is preferably added before the desalting process after grain formation and before the completion of chemical ripening (sensitization).

The amount of addition is chemical ripening (sensitization) from the time of grain formation.
Total amount added up to 1.0 x 1 per mol of silver halide
0 ^-3 mol or more and less than 4.0 × 10 ^-2 mol, preferably 2.0 × 10 ^-3 mol or more and less than 2.0 × 10 ^-2 mol, 4.5 × 10 ^-3 mol or more
It is more preferably less than 1.5 × 10 ^-2 mol.

Next, the silver halide emulsion used in the present invention will be described in detail.

The silver iodobromide emulsion or silver chloroiodobromide emulsion used in the present invention has a silver iodide content of 0.1 to 10 mol%.
And 0.3 to 5.0 mol% is more preferable. The average grain size of these silver halide grains is 0.5 μm or less, preferably 0.
It is in the range of 5 to 0.1 μm.

The present invention is characterized in that these silver halide grains are contained in an amount of 30% or more in terms of projected area, and preferably 50% or more is contained in order to achieve the desired effects of the present invention.

In the present invention, Vcore / Vtotal is 0.3 or less. That is, silver halide grains having a core volume / total volume ratio of silver halide grains of 0.3 or less, and more preferably 0.25 to 0.01 are used.

As the silver halide emulsion in the most preferred embodiment of the present invention, for example, a silver iodobromide emulsion having a silver iodide content of 0.9 mol% and an average grain size of 0.34 μm, or a silver iodide content of An example is a silver iodochlorobromide emulsion having a silver chloride content of 1.0 mol% at 2.0 mol% and an average grain size of 0.41 μm.

The present invention can achieve the intended effect of the present invention by controlling the amount of the thiocyanic acid compound present on the surface of the silver halide grain, and the desired amount of thiocyanate is present on the surface of the silver halide grain. Need to know if they are doing.

The method for quantifying the thiocyanic acid compound contained in the emulsion of the light-sensitive material will be described below (actually see Examples).

1. Determination of thiocyanate ion in emulsion before coating To an emulsion containing 1.5 × 10 ^-2 mol of silver halide, 10 cc of 1% KBr aqueous solution was added and stirred at 40 ° C. for 30 minutes. The emulsion was centrifuged to completely separate the emulsion, and the supernatant was diluted 100 times. Further, the diluted solution was subjected to ultrafiltration, and then thiocyanate ion in the diluted solution was quantified by ion chromatography. For the quantification, a calibration curve prepared separately using an aqueous solution of thiocyanate compound was used.

2. Determination of thiocyanate ion on the surface of silver halide grains in the emulsion before coating Emulsion containing 1.5 × 10 ⁻² mol of silver halide was diluted with 10 cc of distilled water.
The mixture was stirred at 40 ° C for 30 minutes. The emulsion was centrifuged to completely separate the emulsion, and the supernatant was diluted 100 times. Further, the diluted solution was subjected to ultrafiltration, and then thiocyanate ion in the diluted solution was quantified by ion chromatography. For the quantification, a calibration curve prepared separately using an aqueous solution of thiocyanate compound was used.

The amount of thiocyanate ions on the target grain surface was determined by subtracting the value thus obtained from the value of all thiocyanate ions in the emulsion previously obtained. In the present invention, measurement was performed using these two methods.

3. Quantification of thiocyanate ion in the light-sensitive material in a product state The emulsion layer containing 0.1 g of silver was peeled off from the light-sensitive material, and 49 cc
Soak in distilled water. 1 cc of 5% KBr solution in this solution
After addition, ultrasonically stir at 40 ° C for 30 minutes. The solution is centrifuged and the supernatant is filtered. The filtered supernatant is diluted 10-fold and then the thiocyanate ion contained therein is quantified by ion chromatography. For the quantification, a calibration curve prepared separately using an aqueous solution of thiocyanate compound was used.

4. Quantification of thiocyanate ion on the surface of silver halide grains in a light-sensitive material in a product state An emulsion layer containing silver equivalent to 0.1 g was peeled off from the light-sensitive material to obtain 50 cc.
Soak in distilled water.

The solution is ultrasonically stirred at 40 ° C. for 30 minutes. The solution is centrifuged and the supernatant is filtered.
The filtered supernatant is diluted 10-fold and then the thiocyanate ion contained therein is quantified by ion chromatography. The value thus obtained was subtracted from the previously obtained value of thiocyanate ion in the light-sensitive material to obtain the amount of thiocyanate ion on the target grain surface. Even in the case of a multi-layered product, the amount of thiocyanate ions in the target layer can be known by performing peeling for each layer.

For the quantification, a calibration curve prepared beforehand by using an aqueous solution of a thiocyanate compound is used.

The halogenated grains of the silver halide photographic light-sensitive material according to the present invention may be of any crystal type as long as they have the constitution of the present invention, for example, cubic, octahedral,
It may be a single crystal such as a tetrahedron, or may be polytwinned grains having various shapes.

The emulsion used in the silver halide photographic light-sensitive material of the present invention can be produced by a known method. For example, Research Disclosure (RD) No.17643 (December 1978), 22
Can be prepared by the method described in "Emulsion Preparation and Types" on page 23 or the method described in (RD) No. 18716 (November 1979), page 648.

The emulsion used in the silver halide photographic light-sensitive material of the present invention is, for example, "The Theory of the" by TH James.
Photographic process ”4th edition, published by Macmillan (1977
Year) Method described on pages 38-104, GF Duffin, “Photograph
ic Emulsion Chemistry ”, published by Focal Press (1966),
“Chimie et Physique Photographique” by P. Glafkides
Published by Paul Montel (1967) or VL Zelikman et al. “Makin
g And Coating Photographic Emulsion "can be prepared by the method described in Focal Press (1964).

That is, the mixing conditions such as the forward mixing method, the reverse mixing method, the double jet method and the control double jet method under the solution conditions such as the acidic method, the ammonia method and the neutral method,
It can be produced using a particle preparation condition such as a conversion method, a core / shell method, or a combination thereof.

The grain size distribution of silver halide may be either a monodisperse emulsion having a narrow distribution or a polydisperse emulsion having a wide distribution. The crystal structure of silver halide may be composed of different silver halide compositions inside and outside,
For example, a core / shell type monodisperse emulsion having a clear two-layer structure in which a high silver iodide core portion is covered with a low silver iodide shell layer may be used.

The method for producing the above monodisperse emulsion is known, and for example,
J. Phot. Sci, 12.242 to 251, (1963), JP-A-48-36890,
52-16364, 55-142329, 58-49938, British Patent 1,413,748, US Patents 3,574,628, 3,655,394 and the like.

For the emulsion used in the silver halide photographic light-sensitive material of the present invention, for example, a seed crystal is used as a method for obtaining the above monodisperse emulsion, and the seed crystal is used as a growth nucleus to supply silver ions and halide ions. A grown emulsion may be used.

A method for producing the above-mentioned core / shell type emulsion is known, for example, J. Phot. Sci, 24.198. (1976), US Pat.
The methods described in 250, 3,505,068, 4,210,450, 4,444,877 or JP-A-60-143331 can be referred to.

The emulsion used in the silver halide photographic light-sensitive material of the present invention may be tabular grains having an aspect ratio (ratio of grain size / grain thickness) of 3 or more. As an advantage of such tabular grains, it is disclosed in, for example, British Patent No. 2,112,157, U.S. Patents 4,414,310, 4,434,226 etc. as improvement in spectral sensitization efficiency and improvement in image graininess and sharpness can be obtained. The emulsion can be prepared by the methods described in these publications.

The above-mentioned emulsion may be either a surface latent image type which forms a latent image on the grain surface, an internal latent image type which forms a latent image inside the grain, or a type which forms a latent image on both the surface and the inside. It may be an emulsion.

These emulsions are used at the stage of physical ripening or grain preparation, for example, using cadmium salt, lead salt, zinc salt, thallium salt, iridium salt or its complex salt, rhodium salt or its complex salt, iron salt or its complex salt, etc. May be.

The emulsion may be subjected to a Nudel water washing method, a flocculation sedimentation method or the like in order to remove soluble salts. Preferred water washing methods include, for example, aromatic hydrocarbons containing a sulfo group described in JP-B-35-16086. Examples thereof include a method using a system aldehyde resin, and a desalting method using a polymer flocculant such as Exemplified G-3 and G-8 described in JP-A-63-158644.

The emulsion used in the silver halide photographic light-sensitive material of the present invention can use various photographic additives in the steps before and after physical ripening or chemical ripening. Examples of the compound used in such a step include (RD) No. 1 described above.
Various compounds described in 7643, (RD) No. 18716 and (RD) No. 308119 (December 1989) can be used. The types and locations of the compounds described in these three (RD) Research Disclosures are listed below.

Additive RD-17643 RD-18716 RD-308119 Page Classification Page Page Classification Chemical sensitizer 23 III 648 Upper right 996 III Sensitizing dye 23 IV 648-649 996-8 IV A Desensitizing dye 23 IV
998 IV B dye 25-26 VIII 649-650 1003
VIII Development accelerator 29 XXI 648 Upper right fog inhibitor / stabilizer 24 IV 649 Upper right 1006-7 VI Whitening agent 24 V 998 V Hardener 26 X 651 Left 1004-5 X Surfactant 26-27 XI 650 Right 1005 ~ 6 XI Plasticizer 27 XII 650 Right 1006 XII Sliding agent 27 XII Matting agent 28 XVI 650 Right 1008 ~ 9 XVI Binder 26 XXII 1003 ~ 4 IX Support 28 XVII 1009 XVII Used in the silver halide photographic light-sensitive material of the present invention Examples of the support include those described in the above RD,
A suitable support is a polyethylene terephthalate film or the like, and the surface of the support may be provided with an undercoat layer to improve the adhesiveness of the coating layer, or may be subjected to corona discharge or ultraviolet irradiation.

The photographic processing of the light-sensitive material of the present invention is carried out, for example, by RD-17643, XX to XXI, pages 29 to 30 or 308119, XX to X.
Treatment with a treatment liquid may be performed as described in XI, pp. 1011-1010. The treatment temperature is usually in the range of 18 ° C to 50 ° C.

Developers for black and white photographic processing include dihydroxybenzenes (eg hydroquinone), 3-pyrazolidones (eg 1-phenyl-3-pyrazolidone), aminophenols (eg N-methyl-P-aminophenol). Etc. can be used alone or in combination.
It should be noted that the developer may be a known one such as preservative, alkaline agent, p
An H buffer, an antifoggant, a hardener, a development accelerator, a surfactant, an antifoaming agent, a color toning agent, a water softener, a solubilizing agent, a viscosity imparting agent and the like may be used if necessary.

A fixing agent such as thiosulfate or thiocyanate is used in the fixing solution and may further contain a water-soluble aluminum salt such as aluminum sulfate or potassium alum as a hardening agent. In addition, it may contain a preservative, a pH adjuster, a water softener and the like.

[0052]

EXAMPLES The present invention will be specifically described below with reference to examples.

Example 1 [Preparation of seed emulsion] A silver iodobromide containing 2 mol% of silver iodide having an average grain size of 0.27 μm was prepared by the double jet method while controlling at 60 ° C., pAg = 8 and pH = 2.0. A monodisperse cubic emulsion layer was obtained. From the electron micrograph of this emulsion, the generation rate of twin grains was 1% or less in number.

The obtained emulsion was desalted at 40 ° C. with an aqueous solution of demol N (an aldehyde condensate of sodium naphthalene sulfonate) manufactured by Kao Atlas Co., Ltd. and magnesium sulfate, and then desalted into an aqueous gelatin solution. Redispersion gave a seed emulsion A having an average particle size of 0.27 μm.

Further, a seed emulsion B having an average particle size of 0.09 μm was obtained in the same manner.

[Grain Growth from Seed Emulsion] Of this seed emulsion, the amount corresponding to 38.9% of all silver halide used for growth was used as a seed crystal and grown as follows. That is, the seed crystals were dissolved in a solution containing protective gelatin kept at 40 ° C and having an ammonia concentration of 0.16 N, and the seed crystals were further added with glacial acetic acid to obtain p.
H was adjusted to 8.5. Using this solution as a mother liquor, an aqueous 3.2 N ammoniacal silver ion solution and an aqueous halide solution were added by the double jet method, and mixed by stirring.

At this time, a core portion having a high silver iodide mixing ratio was formed under the conditions shown in Table 1 below. Next, the pAg was adjusted to 9.0 and the pH was maintained at 8.5 to form a shell of silver bromide.
-1 Similarly, the monodisperse emulsions E-2 to E-5 shown in Table 1 were prepared. The procedure was the same as for E-1, except for the conditions shown in Table 1.

[0058]

[Table 1]

The resulting five types of emulsions had a total ratio of silver iodide to total silver halide of 2.4 mol%, an average grain size of 0.37 μm and an S / r of 0.12. .

Next, in order to remove excess salts, precipitation desalting was carried out using a demol N aqueous solution (manufactured by Kao Atlas Co.) and an aqueous magnesium sulfate solution to obtain an aqueous gelatin solution containing 9.2 g of ossein gelatin per mol of silver halide. The mixture was added and dispersed by stirring.

Preparation, Treatment and Evaluation of Samples Pure water was added to each of the obtained silver halide emulsions E-1 to E-5 so that the volume per mol of silver was 300 ml, and the temperature was raised to 50 ° C. Spectral sensitizing dyes A and B shown above were added in a weight ratio of 100: 1 so that the total amount was 320 mg per mol of silver halide.

After 10 minutes, ammonium thiocyanate was added in an amount shown in Table 2 per 1 mol of silver, an appropriate amount of chloroauric acid and hypo were added, and 4.5 mg of the following selenium sensitizer was added.
Addition started the chemical ripening.

[0063]

[Chemical 1]

70 minutes before the end of chemical ripening, 3.0 g of AgI fine particles was added per mol of silver, and then 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added to carry out chemical ripening. finished.

To the obtained emulsion, the following additives for emulsion were added to prepare a preparation liquid.

The pH after preparation of the photographic emulsion coating solution was 6.2.
0, the silver potential was adjusted to 80 mV (35 ° C.) using sodium carbonate and potassium bromide solution.

Samples were prepared using this emulsion coating solution as follows. That is, the photographic emulsion layer was prepared so as to have a metal silver equivalent amount of 2.8 g / m ² per side and a gelatin amount of 2.1 g / m ² per side of the photographic emulsion layer.

A protective layer solution was prepared using the additives described below. The protective layer was coated such that the amount of gelatin applied was 0.9 g / m ² . Further, a backing layer coating liquid was prepared by incorporating the additives described below.

Using two slide hopper type coaters to form the emulsion layer and the protective layer prepared above on one side of the support and the backing layer on the side opposite to the emulsion layer, a speed of 80 m / min. Simultaneous coating on both sides was carried out, followed by drying for 2 minutes and 20 seconds to obtain a sample. The backing layer was coated such that the amount of gelatin applied was 2.5 g / m ² . As the support, a copolymer aqueous dispersion obtained by diluting the copolymer consisting of three types of monomers of glycidyl methacrylate 50 wt%, methyl acrylate 10 wt% and butyl methacrylate 40 wt% to 10 wt% was prepared. 17 applied as drawing liquid
An X-ray film for 5 μm was used. This is a polyethylene terephthalate film base colored blue with a concentration of 0.15.

(Spectral sensitizing dye A) 5,5'-dichloro-9-ethyl-3,3'-di- (3-sulfopropyl) -oxacarbocyanine sodium salt anhydride (spectral sensitizing dye B) 5,5'-di- (butoxycarbonyl) -1,
Anhydrous 1'-diethyl-3,3'-di- (4-sulfobutyl) -benzimidazolocarbocyanine sodium salt emulsion The following additives were added to each emulsion. The addition amount is indicated by the amount per mol of silver halide.

Lime-treated inert gelatin 72 g 1,1-dimethylol-1-bromo-1-nitromethane 10 mg t-butyl-catechol 70 mg polyvinylpyrrolidone (molecular weight 10,000) 1.0 g styrene-maleic anhydride copolymer 2.0 g trimethylolpropane 10 g Nitrophenyl-triphenylphosphonium chloride 5 mg 1,3-Dihydroxybenzene-4-ammonium sulfonate 2.0 g 2-Mercaptobenzimidazole-5-sodium sulfonate 1.5 mg 1-Phenyl-5-mercaptotetrazole 15 mg C ₄ H ₉ OCH ₂ CH (OH) CH ₂ N (CH ₂ COOH) ₂ 1.5g Benzyladenine 50mg

[0072]

[Chemical 2]

(Liquid composition of backing layer) 68 g of lime-treated inert gelatin per liter of coating liquid

[0074]

[Chemical 3]

[0075]

[Chemical 4]

Polymethylmethacrylate particles (matting agent having an average particle size of 5 μm) 1.1 g Formalin aqueous solution (35%) 0.8 ml Glyoxal aqueous solution (40%) 0.9 ml Sodium chloride 1 g The additives used for the protective layer are as follows. is there. The added amount is shown as an amount per 1 l of the coating liquid.

Lime-treated inert gelatin 58 g Acid-treated gelatin 2 g Sodium-i-amyl-n-decylsulfosuccinate 1.0 g Polymethylmethacrylate 0.4 g area average particle size matting agent 0.4 g Silicon dioxide particles Area average particle size 1.2 μm Matting agent 0.7 g Ludox AM (DuPont) Colloidal silica 3 g 2,4-dichloro-6-hydroxy-1,3,5-triazine sodium salt 2% aqueous solution (hardening agent) 10 ml Glyoxal 40% aqueous solution (hardening film Agent) 5.0 ml Bis (vinylsulfonylmethyl) ether (hardener) 500 mg

[0078]

[Chemical 5]

The samples thus obtained were evaluated as follows.

(Sensitometry) "New edition / Lighting data book" (Illumination Society of Japan, 1st edition, 2nd edition), page 39, using the standard light B as a light source, and exposing the sample to an exposure time of 0.1
The so-called white exposure was performed with a non-filter exposure at 3.2 CMS for 2 seconds. The sensitivity was obtained from the reciprocal of the amount of light required to increase the blackening density by 1.0, and was shown as the relative sensitivity when the sensitivity of Sample No. 1 was 100.

Further, Dmin is represented by the fog density obtained by subtracting the base density.

The development is performed by the automatic processor SRX-502 (Konica
(Manufactured by Co., Ltd.) using a developer and a fixer having the following compositions and processed in the following steps a and b. The process B is an automatic processor SRX-
I modified the 502.

Processing step Step (a) Step (b) step Processing temperature Processing time Processing temperature Processing time Replenishment amount (° C) (seconds) (° C) (seconds) (common to a and b) Insert -1.2 -0.7 Development + crossover 35 14.6 37 10.5 270 ml / m ² Fixing + crossing 33 8.2 35 7.8 430 ml / m ² Washing + crossing 18 7.2 18 6.3 7.0 l / m ² Squeeze 42 5.7 42 4.3 Dry 48 8.1 53 6.4 Total − 45.0 − 36.0 Developer formulation Part -A (For finishing 15 liters) Potassium hydroxide 470 g Potassium sulfite (50% solution) 3000 g Sodium hydrogencarbonate 150 g Diethylenetriamine pentaacetic acid 5 sodium 45 g 5-Methylbenzotriazole 2.0 g 1-Phenyl-5-mercaptotetrazole 0.2 g Hydroquinone 390 g Water Add 5000ml to finish to 5000ml Part-B (for finishing 15 liters) Glacial acetic acid 220g Triethylene glycol 200g 1-Phenyl-3-pyrazolidone 27g 5-Nitroindazole 0.45g n-Acetyl-DL- Nisylamine 0.15 g Starter (for 1 liter finish) Glacial acetic acid 138 g Potassium bromide 325 g 5-Methylbenzotriazole 1.5 g Add water to make 1 liter Fixer formulation Part-A (for 19 liter finish) Ammonium thiosulfate (70 wt / vol) %) 4000g Sodium sulfite 175g Sodium acetate ・ trihydrate 400g Sodium citrate 50g Gluconic acid 38g Boric acid 30g Glacial acetic acid 140g Part-B (For finishing 19 liters) Aluminum sulfate (anhydrous salt equivalent) 65g Sulfuric acid (50wt%) 105g

[0084]

[Table 2]

As is clear from Table 2, the sample of the present invention has high sensitivity to the comparative sample, and due to the difference in processing steps.
Stable performance was obtained with little influence on Dmin, sensitivity and contrast.

[0086]

According to the present invention, rapid processing is possible, and there is no fog or variation in sensitivity due to the difference in processing steps.
A highly sensitive silver halide photographic light-sensitive material having stable photographic performance was obtained.

Claims (1)

[Claims] 1. A silver halide photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on at least one side of a support, wherein the silver halide emulsion layer has the following (1), ( It is characterized in that the silver iodobromide grains or the silver chloroiodobromide grains satisfying the conditions 2) and 3) are contained in at least 30% or more of the total projected area of silver halide grains present in the same layer. Silver halide photographic light-sensitive material. (1) The average particle size of the silver halide grains is 0.5μm or less (2) thiocyanate amount of compound present in the silver halide grain surface, per mole of silver 1.0 × 10 ^-3 mol to 4.0 × 10 ^- It is less than ² mol. (3) Vcore / Vtotal <0.3 (where Vcore represents the volume of the silver halide grains in the core, and Vtotal represents the volume of the silver halide grains in the final grain size.)