JPH06186671A - Antistatic silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To provide a silver halide photographic sensitive material not causing pressure fog or abrasion without deteriorating the surface smoothness, excellent in transparency and having high antistatic performance even at low humidity. CONSTITUTION:This silver halide photographic sensitive material contains a perovskite compd. and further contains at least one kind of oxide including a metal compd. This oxide is preferably other than a perovskite compd.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a plastic film having an antistatic property improved so as to reduce the influence of humidity change, and in particular, improved so as not to adversely affect photographic characteristics and to prevent pressure and scratches. It relates to a photographic light-sensitive material.

[0002]

2. Description of the Related Art Generally, a plastic film has a strong charging property, and is often restricted in use except for applications utilizing this physical property. For example, a photographic light-sensitive material is a so-called composite material in which a plastic film is generally used as a support having an electrically insulating property, and this support and a photographic light-sensitive material layer are used. Occasionally, they tend to be charged during contact friction or peeling between the same or different material surfaces.

The electrostatic charge accumulated by charging causes many obstacles. The most serious obstacle is that the photosensitive emulsion layer is exposed to light by discharging the electrostatic charge accumulated before the development processing, and when the photographic film is processed for development, dot spots or dendritic spots called so-called static marks are formed. This is to produce feather-like streaks. For example, if this phenomenon appears in a medical or industrial X-ray film or the like, it will lead to a very dangerous judgment. This phenomenon becomes apparent only after development, and is one of the very troublesome problems. Further, these accumulated electrostatic charges may cause a failure such as dust adhering to the film surface or failure in uniform coating on the film surface.

Many failures other than those mentioned above occur due to such charging. For example, in the manufacturing process, it is caused by contact friction between the photographic film and the roller, winding of the photographic film, separation of the support surface from the emulsion surface during the rewinding process, and the like. In the case of finished products, the photographic film may be wound or separated, and the base surface and emulsion surface may be separated from each other, or between the mechanical part or the fluorescent intensifying screen during automatic photographing of X-ray film. It occurs due to contact separation. In addition, it also occurs when it comes into contact with packaging materials.

The static marks of the photographic light-sensitive material, which are induced by the accumulation of such electrostatic charges, become more prominent as the sensitivity of the photographic light-sensitive material increases and the processing speed increases.
Particularly in recent years, the occurrence of static marks has become more likely to occur due to the increasing number of opportunities for severe handling due to the sophistication of photographic light-sensitive materials and high-speed coating, high-speed photography, high-speed automatic processing and the like. Further, dust adhesion after development has become a serious problem in recent years, and improvement to maintain antistatic property after development is required.

The best way to eliminate these static disturbances is to increase the electrical conductivity of the material so that the electrostatic charge can be dissipated in a short time before the stored charge is discharged.

Therefore, conventionally, a method of improving the conductivity of the support of the photographic light-sensitive material and various coated surface layers has been considered,
Attempts have been made to use various hygroscopic substances, water-soluble inorganic salts, certain surfactants, polymers and the like. For example
49-91165 and 49-121523 disclose an example of applying an ionic polymer having a dissociative group in the polymer main chain. In addition, conductive polymers as described in JP-A Nos. 2-9689 and 2-182491, JP-A-63-55541
No. 63-148254, No. 63-148256, and the surfactants described in JP-A No. 1-314191 are known.

However, many of these materials show specificity depending on the type of film support and photographic composition, and give good results for certain film supports and photographic emulsions and other photographic components. , Other different film supports and photographic components not only have no antistatic effect, but can also adversely affect photographic properties. As a more important drawback, many of these substances lose their function as conductive layers under low humidity.

For the purpose of improving the performance deterioration under low humidity, Japanese Patent Publication No. Sho 35-6616 and Japanese Examined Patent Publication No. 1-20735 describe a technique of using a metal oxide as an antistatic treatment agent. In the former, a method using a colloidal sol dispersion is disclosed, and in the latter, a method using a highly crystalline metal oxide powder treated at high temperature for the purpose of improving the conductivity problem of the former. Was disclosed. However, since the latter technique uses powder having high crystallinity, it is stated that it is necessary to consider the particle size and the particle / binder ratio for light scattering.

Further, in JP-A-4-29134, in order to improve not only the performance under low humidity but also other drawbacks, a conductive material used in a photographic light-sensitive material is made of a particulate metal oxide and a fiber. Although a method of using a metal oxide in the form of particles is disclosed, the problem of the amount added remains.

As described above, regarding the photographic light-sensitive material provided with the layer containing the conductive metal fine particles, since the publication of Japanese Patent Publication No. 35-6616, it has been 30 years as a means for improving the performance deterioration under low humidity. Despite the long-term research that has been done, the present is still unsolved.

For example, when a layer containing such conductive metal fine particles is provided in contact with silver halide, there is a problem that pressure fog or scratches are likely to occur on an image due to friction during handling, or a binder is used. When mixed and used, the fine particles existing on the surface fall off due to friction during the manufacturing process or handling, so that there is a problem that the product adhered to the roller and scratches the conveyed product in the manufacturing process.

In order to prevent metal oxide powder from falling off, pressure fog on silver halide and scratches, JP-A-57-104931 discloses a back layer made of crystalline zinc oxide, stannic oxide and indium oxide. It is disclosed to use a metal oxide such as. However, since conductive metal oxides are generally colored, fog due to coloring is a serious problem when incorporated in a light-sensitive material. JP-A-57-104
According to the method described in No. 931, about 1 g of these metal oxides are required as described in the examples, and the coloring (dark blue) thereof is large as fog and greatly impairs photographic performance (transparency). .

[0014]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to solve the above-mentioned problems existing in the past, that is, it does not cause pressure fog and scratches, has excellent transparency, and has high antistatic performance even under low humidity. It is to provide a silver halide photographic light-sensitive material having the same.

[0015]

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

(1) A silver halide photographic light-sensitive material containing a perovskite compound.

(2) A silver halide photographic light-sensitive material containing a perovskite compound and an oxide containing at least one metal element, and the oxide is not a perovskite compound. (3) Perovskite compound, Ni, Ir, Rh, Nb, Ce,
A silver halide photographic light-sensitive material containing an oxide containing at least one metal element selected from Zr, Th and Hf, and the oxide being not a perovskite compound.

(4) Perovskite compound, Zn, Ti,
A silver halide photograph containing an oxide containing at least one metal element selected from Sn, In, Si, Mg, Al, Ba, Mo, W and V, and the oxide is not a perovskite compound Photosensitive material.

(5) The perovskite compound is Zn, Ti, Sn,
The silver halide photographic light-sensitive material according to (2), which contains at least one element selected from In, Si, Mg, Al, Ba, Mo, W and V.

(6) The perovskite compound is Ni, Ir, Rh,
The silver halide photographic light-sensitive material according to (2), containing at least one element selected from Nb, Ce, Zr, Th, Hf, Pb, Fe and Co.

(7) The silver halide photographic light-sensitive material according to any one of (1) to (4), wherein the perovskite compound is a conductor or a semiconductor.

The present invention will be described in more detail below.

As is well known, the conductivity of semiconductors or conductive fine particles is expressed by charge carriers such as cations, anions or electrons, holes present in the particles. Its total electrical conductivity is expressed as:

Σ _t = σ _c + σ _a + σ _n + σ _p σ _c : electric conductivity of cations σ _a : electric conductivity of anions σ _n : electric conductivity of electrons σ _p : electric conductivity of holes When the charge carrier is an ion, it becomes a solid electrolyte, and when the charge carrier is an electron, it becomes a semiconductor. Usually, it is a mixed conductor of both, and a nonstoichiometric compound such as an oxygen-deficient oxide, a metal-excessive oxide, a metal-deficient oxide, or an oxygen-excessive oxide becomes a semiconductor.

As a result of diligent studies on these oxides, the inventor has found that a compound having a large dielectric constant improves the conductivity. And the perovskite compound
The inventors have reached the conclusion that they are particularly suitable as an antistatic agent for photographic light-sensitive materials among oxides, and completed the present invention.

The perovskite compound is a group of compounds having a cation in the center and a face-centered cubic unit cell structure, and is represented by the general formula ABO ₃ . Such a crystal structure is also called a perovskite structure, but it is roughly classified into (1) simple perovskite ... ABO ₃ (2) B-site complex perovskite ... A (B, B ') O ₃ (3) A site composite perovskite can be classified into A, A′BO ₃ , but the compound of the present invention is not limited in any composition as long as the crystal structure is a perovskite structure. For example, CaTiO ₃ , BaTiO ₃ , SrTiO ₃ , CaZrO ₃ , SrSn
O ₃ , SrZrO ₃ , KNbO ₃ , NaNbO ₃ , LaAlO ₃ , YAlO ₃ , KMgF ₃ or Pb (Ti, Zr) O ₃ , K substituted with some metal ions
A compound group such as (Ta, Nb) O ₃ is also included in the perovskite compound. The structure and physical properties of such perovskite compounds are explained in many literatures as seen in Chemical Review No. 37, 1982, Design of Functional Ceramics (Edited by the Chemical Society of Japan).

When the perovskite compound is used as a powder,
The average particle size is 100 μm or less, preferably 10 μm or less. More preferably, if it is 1 μm or less, the transparency can be used without any problem. However, if the average particle size is not 0.0001 μm, the dispersion treatment will be inconvenient.

With respect to the value of volume resistivity, in the case of an oxide from which a large single crystal can be obtained, it means the value of the volume resistivity of the single crystal, and when a large single crystal cannot be obtained, a powder is formed. It means the volume resistivity of the obtained sintered body. If these values are unknown, the value obtained by dividing the volume resistivity of the molded body obtained by applying a constant pressure in the powder state by 10 ² is adopted.

The constant pressure is not particularly limited,
Preferably may 10 kg / cm ² or more pressure, more preferably to adopt a value obtained by dividing the volume resistivity of the material molded over a 100 kg / cm ² or more pressure 10 ^2. The measurement is performed in a dry atmosphere at 25 ° C.

In general, regarding the pressure applied to the powder and the volume resistivity of the molded body, the volume resistivity tends to decrease as the pressure increases. However, even when an isostatic pressure of 3 t / cm ² is applied by a hydrostatic pressure device, a value lower than the volume specific resistance value obtained with a single crystal is not obtained, and the value is about 100 times higher. Therefore, a value obtained by dividing the volume resistivity of the molded body obtained by applying a constant pressure in the powder state by 10 ² is adopted.

[0031] Although the volume resistivity of these perovskite compounds not impose restrictions, preferably as low at room temperature when used in a single composition or a single type, 10 ¹² Omega
cm or less, more preferably 10 ⁷ Ωcm, and particularly preferably 10 ⁵ Ωcm or less.

Examples of the method for producing a layer containing these compounds include frit baking, protective film production methods such as flame spraying, vacuum vapor deposition, sputtering, physical vapor deposition such as ion plating, chemical vapor deposition, and the like. A method for producing an oxide film by an electrophoresis method or a sol-gel method can also be used. Alternatively, after obtaining these perovskite compounds in the form of fine particles, a doctor blade method in which a thin film is formed after dispersion with a suitable binder, or the amount of the binder is increased, and the content of the perovskite compound is 60%.
A method including a coating and drying process using a coating agent suppressed below is preferably used. However, the method of forming the layer containing the perovskite compound in the present invention is not limited to the above-mentioned manufacturing method.

When the perovskite compound particles are used for producing the layer containing the perovskite compound, the particle synthesis method may be any known synthesis method as long as the object of the present invention can be achieved. For example, a method for producing fine particles and ultrafine particles such as a coprecipitation method, a multistage wet method, a sol-gel method, an atomizing method, and a plasma pyrolysis method using a compound containing a metal contained in a target compound composition as a raw material can be mentioned. .

The amount of the perovskite compound added in the case of a coating method using perovskite compound particles and an organic binder is 60% or less, preferably 50% or less, and more preferably 40% as a volume fraction in the polymer after coating and drying.
The following sufficiently achieves the object of the invention. However, from the viewpoint of transparency, the addition amount is preferably smaller, and 30% or less is preferable. More preferably, it may be 20% or less. However, at least a volume fraction of 0.01% or more, preferably 0.1
% Or more must be added. Depending on the compound, it may be necessary to add 1% or more, but the addition amount is not particularly limited to the present invention.

From this volume fraction, good transparency and antistatic property can be obtained, and in addition to the conductive substance, it is used to prevent pressure fog and scratches during handling of the photographic light-sensitive material. The amount is preferably about 0.00005 to 1 g per 1 m ² of the photographic light-sensitive material.

The perovskite compound of the present invention is preferably added to the conductive layer.

The conductive layer containing the perovskite compound of the present invention preferably contains another metal oxide or a conductive polymer compound from the viewpoint of conductivity. As these conductive polymer compounds, for example, polyvinylbenzene sulfonates, polyvinylbenzyltrimethylammonium chloride, quaternary salt polymers, polymer latex and the like are preferable.

The metal oxide is not particularly limited, but an oxide containing at least one metal element selected from Ni, Ir, Rh, Nb, Ce, Zr, Th and Hf is colorless or Since it is white and has high conductivity, the amount of the perovskite compound can be reduced in consideration of problems such as coloring, which is preferable. Or Zn, Ti, Sn, In, Si, Mg, Al, Ba, Mo,
The inclusion of an oxide containing at least one metal element selected from W and V is also preferable in terms of conductivity.

The perovskite compound, metal oxide and conductive polymer compound are used after being dispersed or dissolved in a binder.

The binder used in the present invention is not particularly limited as long as it has a film-forming ability. For example, proteins such as gelatin and casein; carboxymethyl cellulose, hydroxyethyl cellulose, acetyl cellulose, diacetyl cellulose, triacetyl cellulose and the like. Cellulose compounds; saccharides such as dextran, agar, sodium alginate, starch derivatives; polyvinyl alcohol, polyvinyl acetate, polyacrylic acid ester, polymethacrylic acid ester, polystyrene, polyacrylamide, poly-N-vinylpyrrolidone, polyester, polyvinyl chloride , Synthetic polymers such as polyacrylic acid, and the like. In particular, gelatin (lime-processed gelatin,
Acid-treated gelatin, enzyme-degraded gelatin, phthalated gelatin, acetylated gelatin, etc.), acetyl cellulose, diacetyl cellulose, triacetyl cellulose, polyvinyl acetate, polyvinyl alcohol, butyl polyacrylate, polyacrylamide, dextran and the like are preferable.

In the present invention, at least one conductive layer is preferably provided as a constituent layer of the photographic light-sensitive material. . For example, any of a surface protective layer, a back layer, an intermediate layer, an undercoat layer and the like may be used, but two or more layers may be provided if necessary.

The support used in the present invention includes, for example, cellulose nitrate film, cellulose acetate film, cellulose acetate butyrate film, cellulose acetate propionate film, polystyrene film, polyethylene terephthalate film, polycarbonate film and others. There are laminates and the like. More specifically, there may be mentioned a baryta or an α-olefin polymer, particularly a paper coated or laminated with a polymer of an α-olefin having 2 to 10 carbon atoms, such as polyethylene, polypropylene, an ethylene-butene copolymer.

These supports are appropriately selected from transparent ones and opaque ones depending on the intended use of the photographic light-sensitive material. Further, the transparent support is not limited to a colorless and transparent one, but it can be colored and transparent by adding a dye or a pigment.

Further, a polyol compound such as ethylene glycol, propylene glycol or 1,1,1-trimethylolpropane can be added to the protective layer of the present invention or another layer, which also provides a more preferable antistatic effect. Obtainable.

As the light-sensitive material according to the present invention, an ordinary black-and-white light-sensitive material (for example, black-and-white light-sensitive material for photographing, black-and-white light-sensitive material for X-ray
Various photosensitive materials such as black-and-white photosensitive materials for printing) and ordinary multilayer color photosensitive materials (for example, color reversal film, color negative film, color positive film, etc.) can be mentioned. In particular, it is highly effective for high-speed rapid processing silver halide light-sensitive materials and high-sensitivity silver halide light-sensitive materials.

The silver halide photosensitive material according to the present invention will be briefly described below.

As the binder for the photographic layer, proteins such as gelatin and casein, cellulose compounds such as carboxymethyl cellulose, hydroxyethyl cellulose and dextran, agar, sodium alginate, sugar derivatives such as starch derivatives, synthetic hydrophilic colloids such as polyvinyl alcohol, poly -N-vinylpyrrolidone, polyacrylic acid copolymer, polyacrylamide or their derivatives and partial hydrolysates can be used in combination. Gelatin as used herein refers to so-called lime-processed gelatin, acid-processed gelatin and enzyme-processed gelatin.

Other known surfactants may be added to the photographic constituent layers of the present invention alone or as a mixture. Although they are used as coating aids, they are sometimes applied for other purposes such as emulsion dispersion, sensitization and other improvement of photographic characteristics.

The photographic light-sensitive material of the present invention can contain the polymer latex described in US Pat. No. 3,411,911 in the photographic constituent layers.

The silver halide grains in the emulsion may have a regular crystal form such as cubic or octahedral,
Further, it may have an irregular crystal form such as spherical, plate-like, potato-like, etc., or may have a composite form of these crystal forms, and may be a mixture of particles of various crystal forms. . Further, tabular grains having a grain size of 5 times or more the grain thickness are preferably used in the present invention.

In the present invention, the photosensitive silver halide emulsion may be a mixture of two or more kinds of silver halide emulsions. The emulsions to be mixed may differ in grain size, halogen composition, sensitivity and the like. The light-sensitive emulsion may be mixed with a substantially non-light-sensitive emulsion, or may be divided into different layers and used. For example, a spherical or potato-shaped photosensitive emulsion and a photosensitive emulsion composed of tabular grains having a grain size of 5 times or more the grain thickness may be used in the same layer or different layers. When used in different layers, the light-sensitive emulsion comprising tabular grains may be on the side closer to the support or conversely on the side farther from the support.

[0052]

EXAMPLES The present invention will now be described in more detail with reference to examples, but the invention is not limited thereto.

(Production Method of Powder P1) Barium titanyl oxalate BaTiO (C ₂ O ₄ ) ₂ .4H ₂ O 0.02 g of SbO ₂ was added to 20 g, and 85
Heat treatment was performed at 0 ° C. for 5 hours. The obtained powder was pulverized in a zirconia ball mill for 24 hours to obtain a conductive perovskite compound powder having an average particle diameter of 0.5 μm. Put a part of this powder into a thin pressure rubber mold made of latex
After pressurizing and molding with a hydrostatic pressure of 2000 kg / cm ^2, the conductivity was measured by the 4-terminal method, and it was 10 ⁵ Ωcm.

(Production method of powder P2) Barium titanyl oxalate BaTiO (C ₂ O ₄ ) ₂ .4H ₂ O 0.02 g of SbO ₂ was added to 20 g, and 85
Heat treatment was performed at 0 ° C. for 5 hours. 10 g of the obtained powder was added to S
b was ground together with 10 g of crystalline SnO ₂ doped with 1.5% in a zirconia ball mill for 24 hours to obtain a conductive perovskite compound powder having an average particle size of 0.5 μm. Put a part of this powder into a thin pressure rubber mold made of latex
After pressurizing and molding with a hydrostatic pressure of 2000 kg / cm ^2, the conductivity was measured by the 4-terminal method, and it was 10 ⁴ Ωcm.

Example 1 (Preparation of support) * Subbing first layer After biaxially stretching and heat setting, a polyethylene terephthalate film having a thickness of 100 μm was subjected to a corona discharge treatment of 8 W / m ² on one side and then to the other side. As described in JP-A-59-19941, an undercoating coating solution B-1 having the following composition was coated on the surface as a subbing layer B-1 to a dry film thickness of 0.8 μm, and dried at 100 ° C. for 1 minute.
On the surface of the polyethylene terephthalate film opposite to the subbing layer B-1, the undercoating coating solution B-2 having the following composition is dried to a thickness of 0.8 μm as described in JP-A-59-77439. As an undercoat layer B-2, and dried at 100 ° C. for 1 minute.

Subbing coating liquid B-1 Butyl acrylate / t-butyl acrylate / styrene / 2-hydroxyethyl acrylate (30: 20: 25: 25% by weight) copolymer latex liquid (solid content 30%) 270 g Compound A 0.6g Hexamethylene-1,6-bis (ethyleneurea) 0.8g Make up to 1 liter with water.

Undercoat coating solution B-2 Butyl acrylate / styrene / glycidyl acrylate ( 40 : 20 : 40 % by weight) copolymer latex solution (solid content 30%) 270 g Compound A 0.6 g Hexamethylene-1,6- Bis (ethylene urea) 0.8g Make up to 1 liter with water.

* Second subbing layer Further, a corona discharge of 8 W min / m ² was applied to the above subbing layers B-1 and B-2, and a subbing coating solution B-3 having the following composition was formed to a dry film thickness of 0.1. It was applied so as to have a thickness of μm, and dried at 100 ° C. for 1 minute.

Subbing coating solution B-3 Gelatin 10 g Compound A 0.4 g Compound B 0.1 g Silica particles having an average particle size of 3 μm 0.1 g Powder P1 15 g Water is added to make 1 liter.

[0060]

[Chemical 1]

(Preparation of emulsion) Silver halide grains containing 10 ^-5 mol of rhodium per 1 mol of silver were prepared by a control double jet method in an acidic atmosphere of pH 3.0. Grain growth was carried out in a system containing 30 mg of benzyladenine per liter of a 1% aqueous gelatin solution. After mixing with silver and halide, 4-hydroxy-6-methyl-1,3,3a, 7
-Tetrazaindene was added at 600 mg per mol of silver halide, followed by washing with water and desalting.

Then, 60 mg of silver halide per mol
After adding 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene, sulfur sensitization was performed. After sensitization, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added as a stabilizer.

(Silver Halide Emulsion Layer) Additives were prepared and added to the above emulsion in the amounts shown below, and coated on the support.

Latex polymer (styrene / butyl acrylate / acrylic acid terpolymer 1.0 g / m ² tetraphenylphosphonium chloride 30 mg / m ² saponin 200 mg / m ² polyethylene glycol 100 mg / m ² sodium dodecylbenzenesulfonate 100 mg / m ² Hydroquinone 200 mg / m ² Phenidone 100 mg / m ² Sodium styrenesulfonate-maleic acid copolymer (Mw = 250,000) 200 mg / m ² Gallic acid butyl ester 500 mg / m ² Tetrazolium compound 30 mg / m ² 5-Methylbenzotriazole 30 mg / m ² 2-Mercaptobenzimidazole-5-sulfonic acid 30 mg / m ² Inert ossein gelatin (isoelectric point 4.9) 1.5 g / m ² 1- (p-acetylamidophenyl) -5-mercapto tetrazole 30 mg / m ² Silver amount 2.8g / m ²

[0065]

[Chemical 2]

(Emulsion Layer Protective Film) An emulsion layer protective film was prepared and coated in the following coating amounts.

Di (sulfooctyl succinate) 300 mg / m ² Polymethylmethacrylate (average particle size 3.5 μm) 100 mg / m ² Lithium nitrate 30 mg / m ² Acid-treated gelatin (isoelectric point 7.0) 1.2 g / m ² Colloidal silica 50mg / m ² Sodium styrenesulfonate / maleic acid copolymer 100mg / m ² Mordant 30mg / m ² Dye 30mg / m ²

[0068]

[Chemical 3]

(Backing Layer) A backing dye having the following composition was coated on the support on the side opposite to the emulsion layer. The gelatin layer was hardened with glyoxal and 2,4-dichloro-6-hydroxy-s-triazine sodium salt and a hydroxy-containing epoxy compound (d).

Hydroquinone 100 mg / m ² phenidone 30 mg / m ² latex polymer (butyl acrylate / styrene copolymer) 0.5 g / m ² styrene / maleic acid copolymer 100 mg / m ² oxalic acid 40 mg / m ² benzotriazole 100 mg / M ² Styrene sulfonic acid / maleic acid copolymer 100 mg / m ² Lithium nitrate 30 mg / m ² Backing dye (a), (b), (c) 40,30,30 mg / m ² Ocein gelatin 2.0 g / m ²

[0071]

[Chemical 4]

The sample obtained as described above was exposed on the entire surface and developed using the developing solution and the fixing solution shown below, and then a haze test, a surface resistivity test and an antistatic performance test (ash adhesion test). Law).

Developer formulation Hydroquinone 25 g 1-phenyl-4,4-dimethyl-3-pyrazolidone 0.4 g Sodium bromide 3 g 5-Methylbenzotriazole 0.3 g 5-Nitroindazole 0.05 g Diethylaminopropane-1,2-diol 10 g Sulfurous acid Potassium 90g 5-Sodium sulfosalicylate 75g Sodium ethylenediaminetetraacetate 2g Finished to 1 liter with water, pH = 11.5 with sodium hydroxide
Adjusted to.

Fixer formulation (composition A) Ammonium thiosulfate (72.5w% aqueous solution) 240cc Sodium sulfite 17g Sodium acetate trihydrate 6.5g Boric acid 6g Sodium oxalate dihydrate 2g Acetic acid (90w% aqueous solution) 13.6cc ( composition B) pure water (ion-exchanged water) 17 cc sulfuric acid (50 w% aqueous solution) 3.0 g aluminum sulfate (Al ² O ₃ in terms of content 8.1W% aqueous solution) 20 g fixer above composition a in water 500cc when using the composition They were melted in the order of B and finished to 1 liter before use. Of this fixer
The pH was about 5.6.

(Development processing conditions) (Process) (Temperature) (Time) Development 40 ° C 8 seconds Fixing 35 ° C 8 seconds Rinsing at room temperature 10 seconds <Evaluation of antistatic performance: Ash adhesion test method> 23 ° C / 20% RH
Under the conditions described in (1), the emulsion side of the developed sample was rubbed with a rubber roller several times, and tobacco ash was brought close to the film to examine whether it sticks to the film or not according to the following evaluation.

◯: No adhesion even when approaching up to 1 cm ○ △: Adhesion when approaching up to 1 cm to 4 cm △: Adhesion when approaching up to 4 cm to 10 cm ×: Adhesion at 10 cm or more Absent.

<Surface resistivity measuring method> Using a teraohm meter VE-30 manufactured by Kawaguchi Electric Co., Ltd., applied voltage 100V, 23 ° C., 20%
It was measured under the condition of RH.

<Haze Test> After coating the multilayer photographic photosensitive layer,
Turbidimeter made by Tokyo Denshoku Co., Ltd.
The haze was measured by Model T-2600DA and expressed in%.

Example 2 The same procedure as in Example 1 was carried out except that the undercoating coating solution B-4 was used in place of the undercoating coating solution B-3 as the second undercoating layer, and the same evaluation as in Example 1 was carried out. I went.

Subbing coating solution B-4 Gelatin 10 g Compound A 0.4 g Compound B 0.1 g Silica particles having an average particle size of 3 μm 0.1 g Powder P2 5 g Water to make 1 liter.

Example 3 An undercoating coating solution B-3 was prepared in the same manner as in Example 1 except that the undercoating coating solution B-3 was used instead of the undercoating coating solution B-3, and the same evaluation as in Example 1 was carried out. I went.

Subbing coating solution B-5 Gelatin 10 g Compound A 0.4 g Compound B 0.1 g Silica particles having an average particle size of 3 μm 0.1 g Powder P2 3 g Water is adjusted to 1 liter.

Comparative Example 1 An undercoating coating solution B-6 was prepared in the same manner as in Example 1 except that the undercoating coating solution B-3 was used in place of the undercoating coating solution B-3, and the same evaluation as in Example 1 was performed. I went.

Subbing coating solution B-6 Gelatin 10 g Compound A 0.4 g Compound B 0.1 g Silica particles with an average particle size of 3 μm 0.1 g Water to make 1 liter.

Comparative Example 2 An undercoating coating solution B-7 was prepared in the same manner as in Example 1 except that the undercoating coating solution B-3 was used in place of the undercoating coating solution B-3 as the second undercoating layer. I went.

Subbing coating solution B-7 Gelatin 10 g Compound A 0.4 g Compound B 0.1 g Silica particles having an average particle size of 3 μm 0.1 g Powder (crystalline SnO 2) 3 g Water is added to make 1 liter.

The results of Examples 1 to Comparative Example 2 are summarized and shown below.

Volume fraction (%) Surface resistivity (Ω / cm ² ) Antistatic performance Example 1 26 2.5 × 10 ⁷ ○ Example 2 8 1.8 × 10 ⁶ ○ Example 3 5 1.2 × 10 ⁸ ○ Comparative example 1 0 9.5 × 10 ¹³ × Comparative Example 2 5 1.2 × 10 ¹⁰ × From the above results, the effect of the perovskite compound is clear.

Further, it was confirmed that the sample coated with the perovskite compound selected in the present invention remarkably reduced pressure fog and scratches.

[0090]

According to the present invention, a silver halide photographic light-sensitive material having excellent transparency and high antistatic performance even under low humidity conditions can be provided.

Claims (7)

[Claims] 1. A silver halide photographic light-sensitive material containing a perovskite compound. 2. A silver halide photographic light-sensitive material comprising a perovskite compound and an oxide containing at least one metal element, wherein the oxide is not a perovskite compound. 3. A perovskite compound, and Ni, Ir, R
At least 1 selected from h, Nb, Ce, Zr, Th, and Hf
A silver halide photographic light-sensitive material containing an oxide containing one kind of metal element, wherein the oxide is not a perovskite compound. 4. A perovskite compound, and Zn, Ti, S
characterized in that it contains an oxide containing at least one metal element selected from n, In, Si, Mg, Al, Ba, Mo, W and V, and that the oxide is not a perovskite compound. A silver halide photographic light-sensitive material. 5. The perovskite compound is Zn, Ti, Sn, I.
3. At least one element selected from n, Si, Mg, Al, Ba, Mo, W and V is contained.
The described silver halide photographic light-sensitive material. 6. The perovskite compound is Ni, Ir, Rh, N.
3. At least one element selected from b, Ce, Zr, Th, Hf, Pb, Fe and Co is contained.
The described silver halide photographic light-sensitive material. 7. The silver halide photographic light-sensitive material according to claim 1, wherein the perovskite compound is a conductor or a semiconductor.