JP3353156B2 - Antistatic silver halide photographic material - Google Patents

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 improved antistatic property so as to reduce the influence of a change in humidity, and more particularly to a plastic film having no adverse effect on photographic characteristics and having no pressure or scratches. It relates to a photosensitive material.

[0002]

2. Description of the Related Art In general, a plastic film has a strong chargeability, and in many cases, its use is restricted except for applications utilizing such physical properties. For example, a photographic material is generally a plastic film used as a support having an electrical insulating property, and is a so-called composite material composed of this support and a photographic material layer. Occasionally, it is easy to be charged at the time of contact friction or peeling with the surface of the same or different material.

[0003] The electrostatic charge accumulated by charging causes many obstacles. The most serious obstacle is that the photosensitive emulsion layer is exposed due to the discharge of the electrostatic charge accumulated before the development processing, and when the photographic film is processed, so-called spot marks or dendrites called so-called static marks are formed. This is to cause feather-like spots. For example, when this phenomenon appears in medical or industrial X-ray films, it leads to a very dangerous judgment. This phenomenon is evident only after development, and is one of the most troublesome problems. In addition, these accumulated electrostatic charges cause troubles such as attachment of dust to the film surface and inability to perform uniform coating on the film surface.

[0004] Many failures other than those described above occur due to such charging. For example, in a manufacturing process, it is caused by contact friction between a photographic film and a roller, winding of a photographic film, separation of a support surface from an emulsion surface in a rewinding process, and the like. In the finished product, when the photographic film is wound or switched, the base surface and the emulsion surface are separated from each other, or between the mechanical portion or the fluorescent intensifying screen during the automatic photographing of the X-ray film. Occurs due to contact separation. In addition, it also occurs in contact with packaging materials.

[0005] The static mark of the photographic light-sensitive material induced by the accumulation of the electrostatic charge becomes remarkable as the sensitivity of the photographic light-sensitive material increases and the processing speed increases.
In particular, in recent years, static marks have become more liable to be generated due to the sophistication of photographic light-sensitive materials and the increased number of opportunities to receive severe handling such as high-speed coating, high-speed photographing, and high-speed automatic processing. Furthermore, the adhesion of dust after the development processing has been a serious problem in recent years, and there has been a demand for an improvement that maintains the antistatic property even after the development processing.

The best way to eliminate these static interferences 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, a method for improving the conductivity of a support of a photographic light-sensitive material and various coating surface layers has been conventionally considered.
Attempts have been made to use various hygroscopic substances, water-soluble inorganic salts, certain surfactants, polymers, and the like. For example,
JP-A-49-91165 and JP-A-49-121523 disclose examples in which an ionic polymer having a dissociating group in the polymer main chain is applied. Other, JP-A No. 2-9689, conductive polymers as described in JP-A-2-182492, JP-A-63-55541
And surfactants described in JP-A-63-148254, JP-A-63-148256 and JP-A-1-314191 are known.

However, many of these materials exhibit specificity depending on the type of film support and the photographic composition, giving good results for certain film supports and photographic emulsions and other photographic components. In addition, other different film supports and photographic components are not only completely useless for antistatic, but can also adversely affect photographic properties. More importantly, many of these materials lose their function as conductive layers at low humidity.

For the purpose of improving the performance deterioration under low humidity, Japanese Patent Publication No. 35-6616 and Japanese Patent Publication No. 1-20735 describe a technique 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 a high temperature for the purpose of improving the conductivity problem of the former is disclosed. Was disclosed. However, it is stated that the latter technique uses a powder having high crystallinity, so that it is necessary to consider the particle diameter and the particle / binder ratio for light scattering.

Japanese Patent Application Laid-Open No. 4-29134 discloses a method for improving the performance under low humidity as well as improving other disadvantages. Although a method using a metal oxide in the form of a metal has been disclosed, the problem of the addition amount remains.

As described above, photographic photosensitive materials provided with a layer containing conductive metal fine particles have been used as a means for improving performance deterioration under low humidity for 30 years since the publication of Japanese Patent Publication No. 35-6616. Despite these long-term studies, they have not been solved yet.

For example, when a layer containing such conductive metal fine particles is provided in contact with silver halide, there is a problem that pressure fogging or abrasion easily occurs on an image due to rubbing during handling, or a binder may be used. When mixed and used, fine particles present on the surface are dropped off due to friction during the manufacturing process or handling, and thus there is a problem in the manufacturing process that the product adheres to the rollers and is damaged.

In order to prevent powder dropping of metal oxides, pressure fog on silver halide and abrasion, JP-A-57-104931 discloses crystalline zinc oxide, stannic oxide and indium oxide in the back layer. It is disclosed to use a metal oxide such as However, since a metal oxide having conductivity is generally colored, when it is contained in a photosensitive material, fogging due to coloring becomes a serious problem. JP 57-104
According to the method described in No. 931, about 1 g of these metal oxides are required as described in Examples, and the coloring (dark blue) is large as fog and greatly impairs photographic performance (transmission). .

[0014]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to solve the above-mentioned conventional problems, that is, it is free from pressure fog and abrasion, has excellent transparency, and has high antistatic performance even under low humidity. To provide a silver halide photographic light-sensitive material.

[0015]

The above object of the present invention has been attained by the following constitutions.

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

(4) Perovskite compound and 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 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,
(2) The silver halide photographic material as described in (2), which contains at least one element selected from the group consisting of Nb, Ce, Zr, Th, Hf, Pb, Fe, and Co.

(7) The silver halide photographic material as described in any of (1) to (4) above, wherein the perovskite compound is a conductor or a semiconductor.

Hereinafter, the present invention will be described in more detail.

As is well known, the conductivity of semiconductors or conductive fine particles is developed by charge carriers such as cations, anions or electrons and 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 cation σ _a : electric conductivity of anion σ _n : electric conductivity of electron σ _p : electric conductivity of hole 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, the conductor is a mixture of both, and a nonstoichiometric compound such as an oxygen-deficient oxide, a metal-excess oxide, a metal-deficient oxide, or an oxygen-excess oxide becomes a semiconductor.

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

[0026] The perovskite compound, centered on a cation, is written as formula ABO ₃ in compounds having a face-centered cubic unit cell structure. Such a crystal structure is also called a perovskite structure. When roughly classified, (1) simple perovskite... ABO ₃ (2) B-site composite perovskite A (B, B ') O ₃ (3) A-site complex perovskite ... A, A'BO ₃ can be classified, but the compound of the present invention is not limited as long as it has 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 with some metal ions substituted
Compound groups such as (Ta, Nb) O ₃ are also included in the perovskite compounds. The structure and physical properties of such perovskite compounds are described in many literatures as shown 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, it can be used without any problem regarding transparency. In particular, preparing a coating solution using a solvent
If the sedimentation speed becomes a problem when
μm or less is desirable. However, if the average particle size is not more than 0.0001 [mu] m, there is a problem in the dispersion treatment.

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. Means the volume resistivity of the sintered body obtained as a result. These values if unknown, the volume of a powder state constant pressure over-obtained molded body resistivity adopting divided by the 10 ^2.

There is no particular limitation on the constant pressure,
The pressure is preferably 10 kg / cm ² or more, and more preferably, a value obtained by dividing the volume resistivity of a material formed by applying a pressure of 100 kg / cm ² or more by 10 ² is employed. 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 compact, 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 press, a value lower than the volume resistivity value obtained with a single crystal cannot be obtained, and the value is about 100 times higher. Therefore, a value obtained by dividing 10 ² by the volume specific resistance of a compact obtained by applying a constant pressure in a powder state 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, particularly preferably 10 ⁵ Ωcm or less.

The method for producing the layer containing these compounds includes frit baking, a protective film production method such as a flame spraying method, a physical vapor deposition method such as a vacuum vapor deposition method, a sputtering method and an ion plating method, a chemical vapor deposition method, An oxide film production method such as 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 of forming a thin film after dispersing with a suitable binder, or increasing the amount of the binder to reduce the content of the perovskite compound to 60%
A method including a coating and drying process using a coating agent suppressed as described below is preferably used. However, the method for forming the layer containing the perovskite compound in the present invention is not limited to the above-described production method.

In the case of using perovskite compound particles for producing a layer containing a perovskite compound, any known synthesis method may be used as the method for synthesizing the particles, 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 multi-stage 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 exemplified. .

The addition amount of the perovskite compound in the case of using a coating method using perovskite compound particles and an organic binder is 60% or less, preferably 50% or less, more preferably 40% or less by volume in the polymer after coating and drying.
The object of the present invention will be sufficiently achieved in the following. However, from the viewpoint of transparency, it is preferable that the amount of addition is smaller, more preferably 30% or less. More preferably, it may be 20% or less. However, at least 0.01% by volume fraction, preferably 0.1%
% Or more is necessary. 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 properties can be obtained. In addition, not only conductive materials but also pressure fog and scratches during handling of photographic photosensitive materials can be prevented. the amount is about 0.00005~1g per photosensitive material 1 m ² is preferred.

The perovskite compound of the present invention is preferably added to a 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 high molecular compounds, for example, polyvinylbenzene sulfonates, polyvinylbenzyltrimethylammonium chloride, quaternary salt polymers, polymer latex and the like are preferable.

There is no particular limitation on the metal oxide, 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, it is preferable because the amount of the perovskite compound can be reduced in consideration of problems such as coloring. Or Zn, Ti, Sn, In, Si, Mg, Al, Ba, Mo,
It is also preferable to contain an oxide containing at least one metal element selected from W and V from the viewpoint of conductivity.

The perovskite compound, metal oxide and conductive polymer compound are used by 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. Examples thereof include proteins such as gelatin and casein; and binders such as carboxymethylcellulose, hydroxyethylcellulose, acetylcellulose, diacetylcellulose and triacetylcellulose. Cellulose compounds; dextran, agar, sodium alginate, sugars such as starch derivatives; polyvinyl alcohol, polyvinyl acetate, polyacrylate, polymethacrylate, polystyrene, polyacrylamide, poly-N-vinylpyrrolidone, polyester, polyvinyl chloride And synthetic polymers such as polyacrylic acid. In particular, gelatin (lime-processed gelatin,
Acid-treated gelatin, enzyme-decomposed gelatin, phthalated gelatin, acetylated gelatin, etc.), acetyl cellulose, diacetyl cellulose, triacetyl cellulose, polyvinyl acetate, polyvinyl alcohol, polybutyl acrylate, polyacrylamide, dextran and the like are preferable.

In the present invention, it is preferable to provide at least one conductive layer 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 as necessary.

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

These supports are appropriately selected from transparent and opaque ones according to the intended use of the photographic light-sensitive material. The transparent support is not only colorless and transparent, but may be colored and transparent by adding a dye or pigment.

In addition, a polyol compound such as ethylene glycol, propylene glycol, 1,1,1-trimethylolpropane or the like can be added to the protective layer or other layers of the present invention, which also provides a more favorable antistatic effect. Obtainable.

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

Hereinafter, the silver halide photosensitive material according to the present invention will be briefly described.

Examples of binders for the photographic layer include proteins such as gelatin and casein, cellulose compounds such as carboxymethylcellulose, hydroxyethylcellulose and dextran, sugar derivatives such as agar, sodium alginate and starch derivatives, synthetic hydrophilic colloids such as polyvinyl alcohol and polyalcohol. -N-vinylpyrrolidone, polyacrylic acid copolymer, polyacrylamide or derivatives or partial hydrolysates thereof can be used in combination. The gelatin mentioned here refers to so-called lime-processed gelatin, acid-processed gelatin and enzyme-processed gelatin.

Other known surfactants may be added alone or in combination to the photographic constituent layer of the present invention. Although they are used as coating aids, they are sometimes applied for other purposes, such as emulsification and dispersion, sensitization and other improvements in photographic properties.

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

The silver halide grains in the emulsion may have a regular crystal form such as cubic or octahedral,
In addition, those having irregular crystal forms such as spherical, plate-like and potato-like forms, or those having a complex form of these crystal forms may be used, and may be composed of 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. A substantially light-insensitive emulsion may be used as a mixture with the light-sensitive emulsion, or may be used separately in another layer. 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 photosensitive emulsion comprising tabular grains may be on the side closer to the support or, conversely, on the side farther away.

[0052]

Next, the present invention will be described in more detail with reference to Examples, but it should not be construed that the invention is limited thereto.

[0053] The barium titanyl oxalate _{BaTiO (C 2 O 4) 2} · 4H 2 O 20g to SbO ₂ (method of producing a powder P1) was added 0.02 g, 85
Heat treatment was performed at 0 ° C. for 5 hours. The obtained powder was ground in a zirconia ball mill for 24 hours to obtain a conductive perovskite compound powder having an average particle size of 0.5 μm. A part of this powder is put into a thin pressure rubber mold made from latex.
After pressing and molding with a hydrostatic pressure of 2000 kg / cm ^2, the conductivity was measured by a four-terminal method and found to be 10 ⁵ Ωcm.

[0054] The barium titanyl oxalate _{BaTiO (C 2 O 4) 2} · 4H 2 O 20g to SbO ₂ (method of producing a powder P2) was added 0.02 g, 85
Heat treatment was performed at 0 ° C. for 5 hours. 10 g of the obtained powder is
b was pulverized with 10 g of 1.5% -doped crystalline SnO ₂ in a zirconia ball mill for 24 hours to obtain a conductive perovskite compound powder having an average particle size of 0.5 μm. A part of this powder is put into a thin pressure rubber mold made from latex.
After pressing and molding with a hydrostatic pressure of 2000 kg / cm ^2, the conductivity was measured by a four-terminal method and found to be 10 ⁴ Ωcm.

Example 1 (Preparation of Support) * First layer of undercoating: A 100 μm-thick polyethylene terephthalate film after biaxial stretching and heat setting was subjected to a corona discharge treatment of 8 W / m ² on both sides. An undercoating coating solution B-1 having the following composition was applied as a subbing layer B-1 having a dry film thickness of 0.8 μm as described in JP-A-59-19941, and dried at 100 ° C. for 1 minute.
Further, on the surface of the polyethylene terephthalate film opposite to the undercoat layer B-1, an undercoat coating solution B-2 having the following composition as described in JP-A-59-77439 was applied to a dry film thickness of 0.8 μm. Was applied as a subbing layer B-2 and dried at 100 ° C. for 1 minute.

Subbing coating solution 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 (ethylene urea) 0.8g Make up to 1 liter with water.

Undercoating solution B-2 butyl acrylate / styrene / glycidyl acrylate ( 40 : 20 : 40 % by weight) Copolymer latex liquid (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 Subcoating Layer Further, a corona discharge of 8 W / m ² was applied on the subbing layers B-1 and B-2, and a subbing coating solution B-3 having the following composition was dried to a thickness of 0.1. It was applied to a thickness of μm and dried at 100 ° C. for 1 minute.

Undercoating coating solution B-3 10 g of gelatin 0.4 g of compound A 0.1 g of compound B 0.1 g of silica particles having an average particle diameter of 3 μm 0.1 g of powder P1 15 g Finished to 1 liter with water.

[0060]

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

Next, 60 mg of silver halide per mole was used.
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 following amounts, 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 styrene sulfonate-maleic acid copolymer (Mw = 250,000) 200 mg / m ² Butyl gallate 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 of 2.8g / ^{m 2}

[0065]

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

Di (sulfooctyl sulfosuccinate) 300 mg / m ² Polymethyl methacrylate (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 50 mg / m ² Sodium styrene sulfonate / maleic acid copolymer 100 mg / m ² Mordant 30 mg / m ² Dye 30 mg / m ²

[0068]

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(Backing Layer) A backing dye having the following composition was coated on the support opposite to the emulsion layer. The gelatin layer was hardened with glyoxal, 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 Citric 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) 40,30,30mg / m 2 ossein gelatin 2.0 g / m ^Two

[0071]

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The entire surface of the sample obtained as described above was exposed and developed using the following developing solution and fixing solution. Then, a haze test, a surface resistivity test and an antistatic performance test (ash adhesion test) were performed. Method).

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 Sodium 5-sulfosalicylate 75g Sodium ethylenediaminetetraacetate 2g Finished to 1 liter with water, pH = 11.5 with sodium hydroxide
Was adjusted.

Fixing solution formulation (composition A) Ammonium thiosulfate (72.5 w% aqueous solution) 240 cc Sodium sulfite 17 g sodium acetate trihydrate 6.5 g boric acid 6 g sodium citrate dihydrate 2 g acetic acid (90 w% aqueous solution) 13.6 cc ( Composition B) Pure water (ion-exchanged water) 17 cc Sulfuric acid (50 w% aqueous solution) 3.0 g Aluminum sulfate (aqueous solution whose content in terms of Al ₂ O ₃ is 8.1 w%) 20 g The above composition A and composition in 500 cc of water when using a fixing solution Dissolved in the order of B, finished to 1 liter and used. This fixer
pH was about 5.6.

(Development processing conditions) (Process) (Temperature) (Time) Development 40 ° C. for 8 seconds Fixing 35 ° C. for 8 seconds Rinse at room temperature 10 seconds <Evaluation of antistatic performance: Ash adhesion test method> 23 ° C., 20% RH
Under the conditions described above, the emulsion side surface of the developed sample was rubbed several times with a rubber roller, and the tobacco ash was approached to determine whether or not the tobacco ash adhered to the film according to the following evaluation.

○: No adhesion at all when approached to 1 cm ○ △: Adhesion when approached from 1 cm to 4 cm △: Adhesion when approached from 4 cm to 10 cm ×: Adhesion even at 10 cm or more Absent.

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

<Haze Test> After coating the multilayer photographic photosensitive layer,
The unexposed sample was processed for turbidity by Tokyo Denshoku Co., Ltd.
The haze was expressed in% by measuring using Model T-2600DA.

Example 2 The same procedure as in Example 1 was carried out except that the undercoat coating solution B-4 was used instead of the undercoat coating solution B-3 as the second undercoat layer, and the same evaluation as in Example 1 was performed. Was done.

Undercoat Coating Solution B-4 Gelatin 10 g Compound A 0.4 g Compound B 0.1 g Silica particles having an average particle diameter of 3 μm 0.1 g Powder P2 5 g Finished to 1 liter with water.

Example 3 An undercoating solution was prepared in the same manner as in Example 1 except that the undercoating solution B-5 was used instead of the undercoating solution B-3 as the second undercoating layer, and the same evaluation as in Example 1 was performed. Was done.

Undercoating coating solution B-5 10 g gelatin Compound A 0.4 g Compound B 0.1 g Silica particles having an average particle diameter of 3 μm 0.1 g Powder P2 3 g Finished to 1 liter with water.

Comparative Example 1 An undercoating solution was prepared in the same manner as in Example 1 except that the undercoating coating solution B-6 was used instead of the undercoating coating solution B-3 as the undercoating second layer, and the same evaluation as in Example 1 was performed. Was done.

Undercoating coating solution B-6 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 Finished to 1 liter with water.

Comparative Example 2 An evaluation was made in the same manner as in Example 1 except that the undercoating coating solution B-7 was used instead of the undercoating coating solution B-3 as the undercoating second layer. Was done.

Undercoating coating solution B-7 Gelatin 10 g Compound A 0.4 g Compound B 0.1 g Silica particles having an average particle diameter of 3 μm 0.1 g Powder (crystalline SnO 2) 3 g Finished to 1 liter with water.

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

Volume fraction (%) Surface specific resistance (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 10 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 recognized that the sample coated with the perovskite compound selected in the present invention significantly reduced pressure fog and abrasion.

[0090]

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

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-57-104931 (JP, A) JP-A-4-29134 (JP, A) JP-A-4-234757 (JP, A) JP-A 55-49 5982 (JP, A) (58) Field surveyed (Int. Cl. ⁷ , DB name) G03C 1/85

Claims (7)

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