JPH07244355A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To prevent uneven development by rapid processing and the occurrence of a static mark and to attain high sensitivity and high gamma by incorporating saponin and a specified compd. in combination with each other into a constituent layer of a photographic sensitive material. CONSTITUTION:Saponin and a compd. represented by the formula are incorporated in combination with each other into a constituent layer of a photographic sensitive material with a silver halide emulsion layer on the base. In the formula, R1 is 1-30C optionally substd. alkyl, alkenyl or aryl and A is -O-, -S-, -COO-, -N(R1)-, -CON(R1)- or -SO2N(R1)-(where R1 is H or optionally substd. alkyl). The weight ratio between the compd. represented by the formula and saponin is 1:3 to 3:1 and the silver halide emulsion layer preferably contains silver halide particles made of silver iodobromide or silver chloroiodobromide having <=3mol% average silver iodide content.

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 more particularly to a silver halide photographic light-sensitive material having excellent antistatic properties and suppressing uneven development during rapid processing.

[0002]

2. Description of the Related Art In recent years, rapid processing properties as well as high sensitivity and high image quality have been strongly desired for silver halide photographic light-sensitive materials. At the same time, there is a strong demand to reduce the amount of processing waste liquid in order to eliminate pollution. However, when the light-sensitive material is rapidly processed or the processing liquid is reduced, uneven development may easily occur.

On the other hand, a silver halide photographic light-sensitive material has a property of being easily charged with static electricity under a low humidity, and when it is discharged, a fog called "static mark" is generated, which causes a fatal obstacle to an image. Sometimes.

There have been many proposals as an antistatic method in the photographic industry, for example, various surfactants used in other fields or JP-A-48-2.
No. 0785, JP-A-57-104931 and the like in which conductivity is imparted are disclosed.

As a method of eliminating uneven development, it is known to accelerate the developability of the light-sensitive material, for example, silver halide grains are changed to silver chloride, or the swelling degree of the light-sensitive material is increased. Has been. However, when the degree of swelling is increased, the developability is increased, but the drying speed is decreased, which is not suitable for the purpose of rapid processing.

The present inventor examined various activators including polyalkylene oxide compounds known as antistatic agents, and found that antistatic performance was obtained,
It has been found that there is a drawback that uneven development occurs frequently in rapid processing.

There has been a demand for a silver halide photographic light-sensitive material which does not cause development unevenness even when it is rapidly processed with low replenishment, has excellent sensitivity and gradation, and also has antistatic properties.

[0008]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide a high-sensitivity and high-gamma silver halide photographic light-sensitive material which does not cause development unevenness in rapid processing and prevents static marks. It is to be.

[0009]

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

(1) In a silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support, saponin and the following general formula [1] are contained in at least one layer of the light-sensitive material. A silver halide photographic light-sensitive material comprising at least one of the compounds shown in combination.

[0011]

[Chemical 2]

In the formula, R ₁ represents a substituted or unsubstituted alkyl group, alkenyl group or aryl group having 1 to 30 carbon atoms. A is -O -, - S -, - COO -, - N (R 1) -, - CON
(R ₁ )-or -SO ₂ N (R ₁ )-, wherein R ₁ represents a hydrogen atom or a substituted or unsubstituted alkyl group.

(2) The weight ratio of the compound represented by the general formula [1] to the saponin is 1: 1 to 3:
1. The silver halide photographic light-sensitive material according to item (1), which is 1.

(3) The silver halide emulsion layer is characterized by containing silver halide grains composed of silver iodobromide or silver chloroiodobromide having an average silver iodide content of 3 mol% or less (1) )
The silver halide photographic light-sensitive material according to the item (2).

The present invention will be described in detail below.

The silver halide photographic light-sensitive material of the present invention is a silver halide photographic light-sensitive material having a structure having at least one light-sensitive halogen emulsion layer and a protective layer on at least one side of a support.

The saponin according to the present invention and the compound of the general formula [1] are used in the hydrophilic colloid layer of the silver halide photographic light-sensitive material constituting layer of the present invention, specifically, a protective layer, an intermediate layer or an emulsion layer. Used for. Particularly preferably, it is contained in combination in the protective layer on the photosensitive silver halide emulsion layer.

The saponin used in the present invention is a steroidal or triterpene type glycoside distributed in the plant kingdom,
It is a known compound which has been known as a coating aid or a wetting agent for a long time in the photographic industry. The type of saponin used in the present invention can be used without particular limitation, but saponins extracted from Quillaja roots and the like are preferable, and these can be easily obtained as commercial products.

Next, specific examples of the compound represented by the general formula [1] of the present invention will be shown.

[0020]

[Chemical 3]

[0021]

[Chemical 4]

The above compounds can be easily synthesized, for example, by adding ethylene oxide to the corresponding fatty acid monoethanolamide and reacting them.

Commercially available products such as Amizet 5C and Amizet 10C (both manufactured by Nikko Chemical Co., Ltd.) can be used in the present invention as compounds belonging to the general formula [1] of the present invention. In addition to the above, for example, JP-A-52-55521,
The exemplified compounds described in the specification of No. 60-76741 can also be used in the present invention.

As described above, the general formula [1] according to the present invention
Both the compound represented by and saponin are known materials in the photographic industry. However, there is no disclosure regarding the use of both in a photosensitive material constituting layer. According to the study of the present inventor, it was unexpected that the above-described object of the present invention could be achieved by the combination of these two specific amounts.

That is, the ratio of the compound represented by the above general formula [1] and the saponin added is 1: 1 to 3: 1 by weight.
In the range of 1: 1 to 1: 0.5 (2: 1)
Within the range, the desired effects of the present invention are satisfactorily achieved. It has been found that if the ratio is out of this range, the effect of preventing development unevenness and static marks is poor and the photographic performance is not excellent.

The amount used in the silver halide photographic light-sensitive material in the present invention is not uniform depending on the type, form or coating conditions of the light-sensitive material, but it is usually the above ratio per 1 m ^{2 of} silver halide photographic light-sensitive material. The total amount may be 10 mg to 100 mg, preferably 20 mg to 80 mg. To add to the photosensitive material constituent layer, it is dissolved in water or an organic solvent such as methanol, ethanol, acetone or a mixed solution of water and these organic solvents, and then dissolved in the silver halide photographic photosensitive material constituent layer of the present invention. It is added to the hydrophilic colloid layer. It is preferably added in combination in the protective layer on the light-sensitive silver halide emulsion layer. In addition to the addition, a method of spraying, coating or immersing the surfactant on the surface of the silver halide photographic light-sensitive material and then drying it may be used. At this time, other surfactants may be used together to improve the coatability.

The silver halide emulsion layer according to the present invention is an emulsion layer containing silver halide grains composed of silver iodobromide or silver chloroiodobromide having an average silver iodide content of 3 mol% or less. Is preferred. More preferably, the silver iodobromide emulsion layer or silver chloride having an average silver iodide content of 0 mol% to 1.5 mol% is 0 mol%.
The average silver iodide content of .about.10 mol% is 0 to 1.5 mol%.
A mol% silver chloroiodobromide emulsion layer is preferred.

The silver halide emulsion of the silver halide photographic light-sensitive material of the present invention may be silver bromide, silver chlorobromide, or a silver iodochlorobromide emulsion containing a small amount of silver iodide, but is preferable. Is silver chlorobromide, silver iodobromide or silver chloroiodobromide emulsion. The silver halide grain may be of any crystal type as long as it has the constitution of the present invention, for example, a single crystal such as a cube, octahedron or tetrahedron, and has various shapes. It may be polytwinned grains.

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),
It can be prepared by the method described in “Emulsion Preparation and Types” on pages 22 to 23, or the method described in the same (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.

A preferred embodiment of the emulsion used in the silver halide photographic light-sensitive material of the present invention is a monodisperse emulsion in which silver iodide is localized inside the grains. The monodisperse referred to here, when measuring the average particle diameter by a conventional method,
At least 95% by number or weight of grains are silver halide grains having an average grain size within ± 40%, preferably within ± 30%.

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 in which a core portion of high silver chloride is coated with a shell layer of low silver chloride to have a clear two-layer structure may be used.

The method for producing the above-mentioned 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.

The method for producing the above core / shell type emulsion is as follows:
For example, J. Phot. Sci, 24.198. (1976), U.S. Patent 2,592,250.
Nos. 3,505,068, 4,210,450, 4,444,877 and JP-A-60-143331 can be referred to.

The emulsion may be subjected to a Nudel water washing method, a flocculation sedimentation method or the like to remove soluble salts, and a preferable water washing method is, for example, an aromatic hydrocarbon 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-2-7037.

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 to 649 996 to 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 Interface Activator 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 Examples of the support used for the silver halide photographic light-sensitive material 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.

Photographic processing of the light-sensitive material of the present invention can be carried out, for example, by RD-17643, XX-XXI, pages 29-30 or 308119, XX-XX.
I, pp. 1011-1012, treatment with a treatment solution may be performed.

[0040]

EXAMPLES The present invention will now be described in more detail with reference to examples.

Example 1 <Preparation of silver chlorobromide emulsion> An aqueous solution of silver nitrate was added to an aqueous gelatin solution kept at pH = 3.0 and 38 ° C. in the presence of 5.0 × 10 ⁻⁷ mol of iridium (III) chloride per mol of silver. Potassium chloride,
Aqueous potassium bromide solution was added over 60 minutes by the double jet method. During this period, pH was kept at 5.8 and pAg was kept at 7.0. After the addition is complete, p
H was adjusted to 6.0, and 3,3'-diethyl- was used as an infrared sensitizing dye.
5-Methoxy-9,11-neopentylenthiatricarbocyanine iodide 500 mg / mol AgX was added. Further, the mixture was desalted at 40 ° C. using a Demol N aqueous solution manufactured by Kao Atlas Co., and then an aqueous gelatin solution was added and redispersed. A silver chlorobromide emulsion containing a silver bromide / silver chloride ratio of 90:10 mol% was prepared by this method. The obtained emulsion was a cubic monodisperse emulsion having an average grain size of 0.37 μm, which was designated as emulsion Em-1.

Further, potassium iodide was added to an aqueous solution of potassium bromide under the same conditions, and an aqueous solution having a molar ratio of potassium iodide to potassium bromide of 1.26: 98.74 was used instead of the aqueous solution of potassium bromide. Under the same conditions, silver chloroiodobromide grains containing 1.2 mol% of silver iodide were prepared.

The obtained particles were cubic particles having an average particle size of 0.36 μm and were monodisperse particles having a variation coefficient of 11%. This emulsion is E
m-2. Similarly, silver chloroiodobromide emulsions having an average silver iodide content of 2.5 mol% and 5 mol% were prepared by using an aqueous solution in which the molar ratio of potassium iodide and potassium bromide was changed.

All the particles obtained had an average particle size of 0.36 μm.
The particles were cubic monodisperse particles with a coefficient of variation of 13%. This emulsion was designated as Em-3 and Em-4.

Then, the following additives were added per mol of silver halide as described below to prepare an emulsion coating solution.

Nitrophenyltriphenylphosphonium chloride 30 mg Ammonium 1,3-dihydroxybenzene-4-sulfonate 1 g 2-Mercaptobenzothiazole 10 mg Trimethylolpropane 9 g 1,1-Dimethylol-1-bromo-1-nitromethane 10 mg C ₄ H ₉ OCH ₂ CH (OH) CH ₂ N (CH ₂ COOH) ₂ 1g

[0047]

[Chemical 5]

These emulsions were prepared by using 400 g of gelatin as a backing layer, 2 g of polymethacrylate having an average particle size of 6 μm,
Potassium nitrate 24 g, sodium 6 g, dye emulsified dispersion 2 g / 1 m ² per consisting of the following antihalation dye 120g dodecylbenzenesulfonic acid, and the backing layer solution was prepared consisting of glyoxal, glycidyl methacrylate, methyl acrylate, butyl methacrylate copolymer ( (50:10:40 weight ratio) was diluted to a concentration of 10% to obtain a copolymer aqueous dispersion, which was applied as an undercoating liquid to one side of a polyethylene terephthalate base coated with gelatin, a matting agent, Two layers of the emulsion and the protective layer were simultaneously coated with a slide hopper on a backed support obtained by coating with a protective layer consisting of glyoxal and sodium dodecylbenzenesulfonate to obtain a sample.

The saponin according to the present invention and the compound represented by the general formula [1] were added to the emulsion protective layer as shown in Table 1.

The coating amount, 3.0 g / m ² in terms of silver, gelatin weight emulsion layer 2.4 g / m ^2, was protective layer 1.1 g / m ^2. Also, 3.65 g / m ^{2 in} terms of silver, the amount of gelatin is 2.4 g in the emulsion layer.
/ M ² and protective layer 1.18 g / m ² and other samples Nos. 19 and 20 similar to the above were also prepared.

[0051]

[Chemical 6]

(Evaluation of sensitivity and gradation) The obtained sample was 820n
A wedge image was printed with a semiconductor laser beam having a wavelength of m. The temperature at the time of exposure was 40 ° C., and development processing was performed under the following processing steps or conditions to evaluate sensitivity and gradation. The sensitivity was shown as a relative value with the reciprocal of the exposure amount required for giving the density of fog +1.0 in Sample No. 100 taken as 100. The gradation shows the slope of the characteristic curve from fog +0.25 to fog +2.0.

(Evaluation of Development Unevenness) The sample was cut into 127 mm × 305 mm and exposed so that the density after development had three densities of about 1.2, 1.0 and 0.8. The development processing was performed under the conditions, and the occurrence of development unevenness was visually evaluated by the following.

⊚: No unevenness was observed at all ◯: Slight unevenness was observed at Δ: Unevenness was observed but acceptable for practical use ×: Many irregularities were observed and impractical for practical use XX: Conspicuous unevenness (evaluation of antistatic performance [static mark]) 6 cm after conditioning the obtained sample for 1 hour at 23 ° C and 20% RH
The sample cut into 30 cm was brought into contact with a neoprene rubber rod having a diameter of about 30 mm to forcibly rub a certain amount. Then, the static mark was evaluated by visual observation according to the following criteria after the development processing was performed in the same manner as above without exposing.

⊚: No static mark generated ◯: Slightly generated Δ: Slightly generated, but practically usable ×: Many generated, unusable XX: Significantly generated The development was carried out in the following steps using an automatic processor SRX-503 (Konica Corporation) using a developer and a fixer having the following compositions. The process was performed by modifying the automatic processor SRX-503.

Treatment process Process process Process process temperature (° C) Treatment time (sec) Treatment time (sec) Replenishment amount Insertion-1.2 0.8 Development + crossover 35 14.6 9.7 270 ml / m ² Fixing + crossover 33 8.2 5.5 430 ml / m ² Washing with water + Crossover 18 7.2 4.8 7.0 l / min Squeeze 42 5.7 3.8 Dry 48 8.1 5.4 Total −45.0 30.0 Developer formulation Part-A (for finishing 15 liters) Potassium hydroxide 470 g Potassium sulfite (50% solution) 3000 g Sodium hydrogencarbonate 150 g Diethylenetriamine 5 Acetic acid 5 sodium 45 g 5-Methylbenzotriazole 2.0 g 1-Phenyl-5-mercaptotetrazole 0.2 g Hydroquinone 390 g Add water to make up to 5000 ml Part-B (for finishing 15 liters) Glacial acetic acid 220 g Triethylene glycol 200 g 1-phenyl -3-pyrazolidone 27g 5-nitroindazole 0.45g N-acetyl-DL-penicillamine 0.15g starter (for 1 liter finish) glacial acetic acid 138g bromide Lithium 325g 5-Methylbenzotriazole 1.5g Add water to finish to 1 liter Fixer formulation Part-A (for 19 liter finish) Ammonium thiosulfate (70wt / vol%) 4000g Sodium sulfite 175g Sodium acetate / trihydrate 400g Citric acid Sodium 50g Gluconic acid 38g Boric acid 30g Glacial acetic acid 140g Part-B (19 liters finish) Aluminum sulfate (anhydrous salt equivalent) 65g Sulfuric acid (50wt%) 105g Preparation method Part-A and B are mixed to 15 liters 25 after finishing
Adjust the pH to 10.40 at ℃ with acetic acid and NaOH,
Then, 20 cc of a starter is added to make a working solution.

Preparation method of fixer Part-A and B are mixed to make 19 liter, and then the temperature is set to 25.
Use acetic acid and NaOH to adjust the pH to 4.35 at ℃ to make a working solution.

The results obtained are shown in Table 1 below.

[0059]

[Table 1]

As is clear from Table 1, the samples of the present invention have no or little development unevenness and static marks, and there is no deterioration in photographic performance (sensitivity, gradation).

Example 2 <Preparation of silver iodobromide emulsion> (Preparation of seed emulsion Em-5) A hexagonal tabular seed emulsion was prepared by the following method.

Solution A Osein gelatin 60.2 g Distilled water 20 l Polyisopropylene-polyethyleneoxy-disuccinate sodium salt (10% ethanol aqueous solution) 5.6 ml KBr 26.8 g 10% sulfuric acid 144 ml solution B 2.5N AgNO ₃ aqueous solution 3500 ml solution C KBr 1029 g KI 29.3 g Distilled water to 3500 ml Solution D 1.75N KBr aqueous solution At the following potential control amount 35 ° C., use Solution A with the mixing stirrer shown in JP-B-58-58288 and JP-B-58-58289. Solution B and solution C 6 each
Nucleation was performed by adding 4.1 ml by the simultaneous mixing method over 2 minutes.

After stopping the addition of Solution B and Solution C, 60
The temperature of solution A was raised to 60 ° C. over a period of time, and solution B and solution C were again added by the simultaneous mixing method at a flow rate of 68.5 ml / min for 50 minutes. During this period, the silver potential (measured with a silver ion selective electrode using a saturated silver-silver chloride electrode as a reference electrode) was controlled to be +6 mV using the solution D.

After the addition was completed, the pH was adjusted to 6 with 3% KOH, and desalting and washing with water were immediately performed. The obtained emulsion was used as seed emulsion E.
m-5. In this emulsion, 90% or more of the total projected area of silver halide grains is composed of hexagonal tabular grains having a maximum adjacent side ratio of 1.0 to 2.0, the average thickness of hexagonal tabular grains is 0.07 μm, and the average diameter (converted to a circle diameter) is It was found to be 0.5 μm by an electron microscope.

(Preparation of Tabular Emulsion) A tabular silver iodobromide emulsion Em-6 containing 1.20 mol% of AgI was prepared using the following four kinds of solutions.

Solution A Ossein gelatin 29.4 g, seed emulsion Em-0 1.6 mol equivalent Polyisoropyrene-polyethyleneoxy-disuccinate sodium salt (10% ethanol aqueous solution) 3.0 ml Distilled water to 1400 ml Solution B 3.5N AgNO ₃ 2360ml Solution C KBr 970g KI 22.8g Distilled water to 2360ml Solution D 1.75N KBr Aqueous solution Below, at the silver potential control amount 60 ° C, as in the above, Japanese Patent Publication Nos. 58-58288 and 58-582.
Using the mixing stirrer shown in No. 89, the total amount of solution B and solution C was mixed into solution A by a simultaneous mixing method at a flow rate of 21.26 ml / min.
It took 111 minutes to add and grow. During this period, the silver potential was controlled to be +28 mV by using the solution D. After the addition is completed, the following spectral sensitizing dyes (A) and (B) are added.
Were added at 300 mg and 15 mg, respectively, per mol of silver halide.

Next, in order to remove excess salts, precipitation desalting was carried out using an aqueous solution of Demol N (manufactured by Kao Atlas Co., Ltd.) and an aqueous solution of magnesium sulfate to obtain ossein gelatin 9
An aqueous gelatin solution containing 2.2 g was added and dispersed by stirring. Table 1 shows the results of observing and measuring about 3000 particles of Em-6 with an electron microscope and analyzing the shape.

Sensitizing dye (A) 5,5'-dichloro-9-ethyl-3,3'-di- (3-sulfopropyl) oxacarbocyanine sodium salt anhydride Sensitizing dye (B) 5,5 ′ -Di- (butoxycarbonyl) -1,1′-diethyl-3,3 ′
-Anhydrous di- (4-sulfobutyl) benzimidazolocarbocyanine sodium salt Under the conditions for preparing Em-6, AgI content was changed by changing the KI amount of solution C and the silver potential control value using solution D. Of tabular silver bromide emulsions Em-7, Em-8, and Em-9 were prepared by changing the amount of each to 0 mol%, 2.5 mol%, and 5.0 mol%.
As a result of observing 3000 grains of the obtained emulsion with an electron microscope, an average projected area diameter of 1.80 μm and an average grain thickness of 0.35 μm
It was a hexagonal tabular grain with m and a coefficient of variation of 13.

For each of the prepared emulsions, JP-A-2-30
No. 1744, page 95, line 16 to page 96, line 20 and the Ludox AM described below were added in an amount of 10 g per mol of silver halide. Further dye emulsion dispersion shown below
1.2 g was added to make an emulsion coating solution.

Preparation Method of Dye Emulsion Dispersion 10 kg of the following dye was dissolved in a solvent consisting of 28 liters of tricresylphosphite and 85 liters of ethyl acetate at 55 ° C.
This is called an oil-based solvent. On the other hand, a 9.3% gelatin aqueous solution containing 1.35 kg of an anionic surfactant (AS) is called an aqueous solvent.

Next, the oil-based solvent and the water-based solvent were placed in a dispersion pot and dispersed while keeping the liquid temperature at 40 ° C.

[0072]

[Chemical 7]

The additives used for the protective layer are as follows. The added amount is shown as an amount per 1 liter of the coating liquid.

Coating liquid for protective layer Lime-treated inert gelatin 68 g Acid-treated gelatin 2 g Sodium-i-amyl-n-decylsulfosuccinate 0.3 g Polymethylmethacrylate (matting agent having an area average particle size of 5.0 μm) 1.1 g Silicon dioxide particles (Matting agent having an area average particle size of 3.0 μm) 0.5 g Ludox AM (DuPont colloidal silica) 30 g Glyoxal 40% aqueous solution (hardening agent) 1.5 ml (CH ₂ = CHSO ₂ CH ₂ ) ₂ O (hardening agent) 500 mg The saponin according to the present invention and the compound represented by the general formula [1] were added to the emulsion protective layer as shown in Table 2.

[0075]

[Chemical 8]

The emulsion layer has a silver conversion value of 1.7 per side.
^{g / m 2, 2.5g / m} 2 as a weight with a gelatin protective layer is glycidyl methacrylate at a speed per minute 90m by two slide hopper type coater so that the 0.99 g / m ² as a weight with gelatin - methyl acrylate -Butylmethacrylate copolymer (50: 10: 40wt%) diluted to 10wt% to obtain an aqueous copolymer dispersion, which was applied as an undercoating solution on a 175μm polyethylene terephthalate base emulsion A layer and a protective layer were simultaneously coated on both sides and dried for 2 minutes and 15 seconds to obtain a sample.

(Evaluation) The obtained sample was tested at a temperature of 30 ° C. and RH50.
% For 1 day, then sandwiched with an intensifying screen for X-ray photography, KO-250 (manufactured by Konica Corporation), and irradiated with X-ray through Penetrometer B type (manufactured by Konica Medical Corporation). The same development process as in Example 1 was performed to determine the sensitivity and gradation.

The sensitivity was shown as a relative value with the reciprocal of the exposure energy amount required for giving the density of fog +1.0 of Sample No. 21 taken as 100. The gradation is from fog +0.25 to fog +2.
The slope of the characteristic curve up to 0 is shown. The development unevenness and static marks were evaluated in the same manner as in Example 1. The results obtained are shown in Table 2 below.

[0079]

[Table 2]

As is clear from Table 2, even when the emulsion is changed to a silver iodobromide emulsion, the sample of the present invention does not deteriorate the photographic performance (sensitivity, gradation) and the development unevenness and the static mark are not deteriorated. It can be seen that the generation is suppressed.

[0081]

According to the present invention, it is possible to provide a high-sensitivity and high-gamma silver halide photographic light-sensitive material which does not cause development unevenness in rapid processing and prevents the generation of static marks.

Claims (3)

[Claims] 1. A silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support,
A silver halide photographic light-sensitive material characterized by containing saponin and at least one compound represented by the following general formula [1] in combination in at least one of the light-sensitive material constituent layers. [Chemical 1] In the formula, R ₁ represents a substituted or unsubstituted alkyl group, alkenyl group or aryl group having 1 to 30 carbon atoms. A is -O
-, - S -, - COO -, - N (R 1) -, - CON (R 1) -, - SO 2 N
(R ₁ )-represents any group, and R ₁ represents a hydrogen atom or a substituted or unsubstituted alkyl group. 2. The halogenation according to claim 1, wherein the weight ratio of the compound represented by the general formula [1] to the saponin is 1: 1 to 3: 1. Silver photographic light-sensitive material. 3. The silver halide emulsion layer contains silver halide grains consisting of silver iodobromide or silver chloroiodobromide having an average silver iodide content of 3 mol% or less. 1
Alternatively, the silver halide photographic light-sensitive material according to claim 2.