JPH06161038A - Silver halide photographic sensitive material subjected to antistatic treatment - Google Patents

Abstract

PURPOSE:To provide the photographic sensitive material having excellent transparency and high antistatic performance even under low humidity without impairing the smoothness of the surface, without generating the powder dislodgment of an antistatic agent and without generating pressure fogging and rubbing flaws at the time of subjecting this material to an antistatic treatment by using the oxide particles of metals. CONSTITUTION:This photographic sensitive material has photosensitive silver halide emulsion layers on at least one side of a base. The photographic sensitive material has at least one layer of layers having an electrical conductivity on its one side and the materials to be incorporated into the layers having the electrical conductivity contain at least one kind of the elements selected from Ni, Ir, Rh, Nb, Ce, Zr, Th and Hf and at least one kind of oxides having <=10<10>OMEGAcm specific volumetric resistivity of the oxides. The oxides are otherwise the oxides contg. at least one kind of the elements selected from Zn, Ti, Sn, In, Si, MO, W and V.

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 particularly to prevent the occurrence of pressure and scratches without adversely affecting photographic characteristics. The present invention relates to an improved 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 the purpose of 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, it is prone to being charged during contact friction or peeling between surfaces of the same or different materials. 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 process, and when the photographic film is processed for development, it is a dot-shaped spot or so-called static mark. It is the formation of dendritic and feather-like spots.
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 described above occur due to such charging. For example, in the manufacturing process, contact friction between the photographic film and the roller or winding of the photographic film,
It is caused by separation of the support surface and the emulsion surface during the rewinding process. In the case of finished products, the photographic film is wound and the base surface and emulsion surface are separated when switching is performed, or contact is made between the mechanical part during X-ray film automatic photography or the fluorescent intensifying screen. It is caused by separation etc. It also occurs when it comes into contact with other packaging materials. The static marks of the photographic light-sensitive material, which are induced by the accumulation of such electrostatic charges, become more noticeable as the sensitivity of the photographic light-sensitive material increases and the processing speed increases. Particularly in recent years, the development of photographic light-sensitive materials and the increasing opportunities for severe handling due to high-speed coating, high-speed photography, high-speed automatic processing, and the like have made static marks more likely to occur.

Further, the adhesion of dusts after the development process has become a big problem in recent years, and improvement to maintain the antistatic property after the development process 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 a support of a photographic light-sensitive material or various coated surface layers has been considered, and various hygroscopic substances, water-soluble inorganic salts, certain surfactants,
Attempts have been made to use polymers and the like. For example, JP-A-49
-91165 and 49-121523 disclose examples of applying an ionic polymer having a dissociative group in the polymer main chain. Other JP-A No. 2-9689, conductive polymers as described in JP-A No. 2-182491, JP-A-63-55541,
JP-A 63-148254, JP-A 63-148256, JP-A 1-3141
Inventions and the like relating to surfactants such as those described in No. 91 are known.

However, many of these materials show specificity depending on the type of film support and photographic composition, and give good results to 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. More importantly, many of these materials lose their function as conductive layers under low humidity.

For the purpose of improving the performance deterioration under low humidity, JP-B-35-6616 and JP-B-1-20735 describe a technique of using a metal oxide as an antistatic treatment agent. The former technique discloses a method using a colloidal sol dispersion, and the latter technique uses a highly crystalline metal oxide powder treated at high temperature for the purpose of improving the conductivity problem of the former. The method of use has been disclosed. However, since the latter technique uses powder having high crystallinity, it is described that it is necessary to consider the particle diameter and the particle / binder ratio, etc., for light scattering. Further, in JP-A-4-29134, in order to improve not only the performance under low humidity but also other drawbacks, conductive materials used for photographic light-sensitive materials include a particulate metal oxide and a fibrous metal. Although a method using an oxide is disclosed, the problem of the amount added remains.

[0008]

As described above, with respect to the photographic light-sensitive material provided with the layer containing the conductive metal fine particles, since the publication of Japanese Examined Patent Publication No. Sho 35-6616, the deterioration of performance under low humidity has occurred. Despite being studied for more than 30 years as a means of improvement, it is still unsolved.

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

In order to prevent metal oxide powder from falling off, pressure fog on silver halide and scratches, JP-A-57-104931
Japanese Patent Laid-Open Publication No. 2000-242242 discloses that crystalline metal oxides such as zinc oxide, stannic oxide and indium oxide are used for the back layer. However, since metal oxides having conductivity are generally colored, when contained in a light-sensitive material, fog due to coloring causes a serious problem. 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) is fog, and the photographic performance (transparency) is large.
It is something that damages.

[0011]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide a photographic light-sensitive material having excellent anti-static properties even under low humidity, which is excellent in transparency without generation of powder of the antistatic agent, pressure fog and scratches. Is to provide.

A further object of the present invention is to prevent the electrification using metal oxide particles without impairing the smoothness of the surface and preventing the powder of the antistatic agent from falling off.
It is an object of the present invention to provide a photographic light-sensitive material which is excellent in transparency without pressure fog and scratches and has high antistatic performance even under low humidity.

[0013]

The above object of the present invention is to provide N
At least one oxide containing at least one element selected from i, Ir, Rh, Nb, Ce, Zr, Th, and Hf, and having a volume resistivity of 10 ¹⁰ Ωcm or less. A photographic light-sensitive material characterized by containing a seed, or the oxide is Zn, Ti, Sn, In, Si, M
It is achieved by a silver halide photographic light-sensitive material characterized by being an oxide containing at least one element selected from o, W and V.

This is to solve the above-mentioned problems existing in the past by using a compound having a specific element.

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

Here, in general, a semiconductor means a material having a volume resistivity of less than 10 ¹² Ωcm, and a conductor means a material having a volume resistivity of less than 10 Ωcm.

Σ _t = σ _c + σ _a + σ _n + σ _p σ _c cation electrical conductivity σ _a anion electrical conductivity σ _n electron electrical conductivity σ _p hole electrical conductivity When it 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. Although the conductivity of metal oxides is achieved by such a mechanism, many metal oxides have coloring problems.
As a result of diligent study on this coloring problem, the inventor has found that Ni,
The color of the oxide containing at least one element selected from Ir, Rh, Nb, Ce, Zr, Th, and Hf depends on the nonstoichiometric compound such as when oxygen is higher or lower than the stoichiometric ratio. As a result of finding a material having conductivity and being white or colorless and examining it as an antistatic agent, it was concluded that it is suitable as a silver halide photographic light-sensitive material, and the present invention was completed.

That is, the present invention relates to Ni, Ir, Rh, N
To provide a silver halide photographic light-sensitive material characterized in that at least one layer containing an oxide containing at least one element selected from b, Ce, Zr, Th and Hf is provided. is there. A method for producing a layer containing this oxide and a method for producing a protective film such as frit baking, flame spraying,
A physical vapor deposition method such as a vacuum vapor deposition method, a sputtering method, an ion plating method, a chemical vapor deposition method, an electrophoretic method, or a sol-gel method can be used to produce an oxide film. Alternatively, after obtaining these oxides in the form of fine particles, a doctor blade method in which a thin film is formed after dispersion with a suitable binder, or by increasing the amount of binder and coating the oxide content to 60% or less A method including a coating / drying process using an agent is preferably used. But,
The method for forming the oxide-containing layer in the present invention is not limited to the above-mentioned production method as long as the object of the invention is not impaired.

Next, the oxide of the present invention will be described.
Oxides such as HfO ₂ , ThO ₂ , ZrO ₂ and CeO ₂ , N
Oxygen-rich oxides such as b ₂ O _{5 + x} , RhO _2-x , Ir ₂
Oxygen-deficient oxides such as O _3−x and nonstoichiometric hydroxides such as Ni (OH) _x can be cited. Other than these oxides, a composite oxide in which other elements are combined can be used in the present invention as long as the object of the present invention is not impaired.

The combination of these oxides or composite oxides with other oxides can also achieve the object of the invention. As an example of the oxide to be combined, Zn
O, TiO ₂ , SnO ₂ , Al ₂ O ₃ , In ₂ O ₃ , Si
O ₂ , MgO, BaO, MoO ₂ , V ₂ O _{5 and the} like, or composite oxides thereof are preferable, and ZnO, TiO ₂ and SnO ₂ are particularly preferable. Examples of containing different kinds of atoms include, for example, addition of Al and In to ZnO, addition of Nb and Ta to TiO ₂ , and S addition to SnO ₂ .
It is effective to add b, Nb, a halogen element or the like. The added amount of these heteroatoms is preferably in the range of 0.01 mol% to 25 mol%, and particularly preferably in the range of 0.1 mol% to 15 mol%.

The volume resistivity of these oxides is 10 ¹⁰
It is preferably Ωcm or less or 10 ⁷ Ωcm or less, particularly 10 ⁵ Ωcm or less.

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, powder is formed. It means the volume resistivity of the sintered body obtained by the above. When these values are unknown, a value obtained by dividing the volume resistivity of the molded body obtained by applying a constant pressure in a powder state by 10 ² is adopted. The constant pressure is not particularly limited,
A pressure of 10 kg / cm ² or more is preferable, and a value obtained by dividing the volume resistivity of the material formed by applying a pressure of 100 kg / cm ² or more by 10 ² is more preferable. With respect to the pressure applied to the powder and the volume resistivity of the molded body, the volume specific paper tends to decrease as the pressure increases. However, even when an isostatic pressure of 3 t / cm ² is applied with 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.

In producing the layer containing the oxide,
When the oxide particles are used, the synthesis method may be any method as long as the object of the present invention can be achieved by a known synthesis method. Examples thereof include a method for producing fine particles and ultrafine particles such as a coprecipitation method using a transition metal or a compound containing a transition metal as a raw material, a multistage wet method, a sol-gel method, an atomizing method, and a plasma pyrolysis method. Here, the transition metal or the compound containing a transition metal means Ni, Ir, Rh, Nb, Ce, Zr, T depending on the powder synthesis method.
h, Hf, Zn, Ti, Sn, Al, In, Si, M
a compound containing g, Ba, Mo, W and V as main components,
Preferably a water-soluble or organic solvent-soluble compound,
For example, water-soluble metal salts such as FeSO ₄ 7H ₂ O and CuSO ₄ , transition metal compounds soluble in organic solvents such as NiCl ₂ and PdCl ₂ , metal alkoxides such as Ti (OC ₃ H ₇ ) ₄ and ferrocene such as Organic metal compounds and the like are selected, but Ni, Ir, Rh, Nb, C are selected depending on the powder synthesis method.
e, Zr, Th, Hf, Zn, Ti, Sn, Al, I
It is possible to use a material containing n, Si, Mg, Ba, Mo, W, and V as a main component and solid at room temperature, and the powder raw material is not particularly limited.

The average particle size of the oxide particles is preferably 100 μm or less, more preferably 10 μm or less. Further, when the thickness is 1 μm or less, the transparency can be used without any problem. However, if the average particle size is not 0.0001 μ or more, there will be a problem in dispersion.

The amount of addition in the case of a coating method using oxide particles and an organic binder is 60% or less, preferably 50% or less, more preferably 40% or less in terms of volume fraction in the polymer after coating and drying. The object of the invention is sufficiently achieved with. However, such a powder is preferably added in a smaller amount in the first place, and is therefore preferably 30% or less. More preferably, it may be 20% or less. However, the volume fraction is 0.
It is necessary to add 01% or more, preferably 0.1% or more. Depending on the compound, it may be necessary to add 1% or more,
The addition amount is not particularly limited to the present invention.

From this volume fraction, the amount used is about 0.00005 to 1 g per 1 square meter of the photographic light-sensitive material, whereby good transparency and antistatic property can be obtained, and pressure fog, scratches, etc. during handling of the photographic light-sensitive material can be obtained. Can be prevented.

With respect to pressure fog, scratches, etc., it was found that the sample of the present invention in which the oxide selected in the present invention was applied in the form of fine particles was excellent.

The layer containing the metal oxide of the present invention may contain a conductive polymer compound. These compounds are preferably polyvinylbenzene sulfonates, polyvinylbenzyltrimethylammonium chloride, quaternary salt polymers, polymer latices and the like.

The metal oxide powder and the 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. For example, proteins such as gelatin and casein, carboxymethyl cellulose, hydroxyethyl cellulose,
Cellulose compounds such as acetyl cellulose, diacetyl cellulose, triacetyl cellulose, dextran,
Agar, sodium alginate, sugars such as starch derivatives, polyvinyl alcohol, polyvinyl acetate, polyacrylic acid ester, polymethacrylic acid ester, polystyrene,
Examples thereof include synthetic polymers such as polyacrylamide, poly-N-vinylpyrrolidone, polyester, polyvinyl chloride, and polyacrylic acid.

In particular, gelatin (lime-processed gelatin, acid-processed gelatin, enzyme-decomposed 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 containing conductors or semiconductor particles is provided as a constituent layer of the photographic light-sensitive material. For example, a surface protective layer, a back layer,
Any of an intermediate layer and an undercoat layer may be used, but two or more layers may be provided if necessary.

Examples of the support used in the present invention include a cellulose nitrate film, a cellulose acetate film, a cellulose acetate butyrate film, a cellulose acetate propionate film,
There are polystyrene film, polyethylene terephthalate film, polycarbonate film, and other laminated products thereof. More specifically, a baryta or an α-olefin polymer, particularly polyethylene, polypropylene, an ethylene-butene copolymer, etc., having an α of 2 to 10 carbon atoms.
-Paper coated with or laminated with an olefin polymer or the like can be used.

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, and by doing so, more preferable antistatic property can be obtained. You can get the effect.

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

The silver halide light-sensitive material according to the present invention will be briefly described below.

As the binder for the photographic layer, proteins such as gelatin and casein, carboxymethyl cellulose,
Hydroxyethyl cellulose, cellulose compounds such as 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 derivatives thereof and A partial hydrolyzate or the like can be used in combination.

The gelatin referred to herein means 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 a cube or an octahedron, or may have an irregular crystal form such as a sphere, a plate or a potato. Alternatively, it 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 for use. For example, it may be used in the same layer as or in a layer different from the photosensitive silver halide emulsion comprising a spherical or potato-like photosensitive emulsion and a tabular grain having a grain size of 5 times or more the grain thickness. When used in different layers, the light-sensitive silver halide emulsion consisting of tabular grains may be on the side closer to the support or conversely on the far side.

[0044]

EXAMPLES The present invention will now be described in more detail by way of examples, which should not be construed as limiting the present invention.

Example 1 (Preparation of support) 8 W / m on both sides of a polyethylene terephthalate film having a thickness of 100 μm after biaxial stretching and heat setting
² corona discharge treatment was applied to one surface
As described in No. 1, apply the undercoating liquid B-1 below to a dry film thickness of 0.8.
The undercoat layer B-1 was applied so as to have a thickness of μm and dried at 100 ° C. for 1 minute. On the surface opposite to the subbing layer B-1 of the polyethylene terephthalate film, the undercoating coating solution B-2 described below was dried to a thickness of 0.8 .mu.m as described in JP-A-59-77439.
As an undercoat layer B-2, and dried at 100 ° C. for 1 minute.

* Undercoating first layer <Undercoating coating liquid B-1> Copolymer latex of 30% by weight of butyl acrylate, 20% by weight of t-butyl acrylate, 25% by weight of styrene and 25% by weight of 2-hydroxyethyl acrylate Liquid (solid content 30%) 270 g Compound A 0.6 g Hexamethylene-1,6-bis (ethyleneurea) 0.8 g Water is made up to 1 liter.

<Undercoating coating liquid B-2> Copolymer latex liquid containing 40% by weight of butyl acrylate, 20% by weight of styrene and 40% by weight of glycidyl acrylate (solid content 30%) 270 g Compound A 0.6 g Hexamethylene-1 0.8 g of 6,6-bis (ethylene urea) Make up to 1 liter with water.

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

<Undercoating Coating Liquid 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 (RhO _{2 -X} ) 15 g Water is made up to 1 liter.

[0050]

[Chemical 1]

(Emulsion preparation) Grains containing rhodium in an amount of 10 ^-5 mol per mol of silver were prepared by a control double jet method under 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. 6-after mixing with silver and halide
Methyl-4-hydroxy-1,3a, 3,7-tetrazaindene was added in an amount of 600 mg per mol of silver halide, followed by washing with water and desalting.

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

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

Latex polymer: styrene-butyl acrylate-acrylic acid terpolymer Copolymer 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 mercaptotetrazole 30 mg / m ² Silver amount 2.8g / m ²

[0055]

[Chemical 2]

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

Fluorinated dioctyl sulfosuccinate 300 mg / m ² matting agent: 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 50 mg / m ² Sodium styrenesulfonate-maleic acid copolymer 100 mg / m ² Mordant 30 mg / m ² Dye 30 mg / m ²

[0058]

[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 1-oxy-3,5-dichloro-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) Ocein gelatin 2.0 g / m ²

[0061]

[Chemical 4]

The sample obtained as described above was exposed on the whole surface and developed using the developing solution and the fixing solution shown below, and then a haze test, a surface resistivity test and an ash adhesion test method were performed. The results are shown in Table-1.

<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 90 g of potassium sulfite 5-sodium 5-sulfosalicylate 75 g Sodium ethylenediamine tetraacetate 2 g Water was made up to 1 liter.

The pH was adjusted to 11.5 with caustic soda.

<Fixing Solution Formulation> (Composition A) Ammonium thiosulfate (72.5 w% aqueous solution) 240 ml 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 ml (Composition B) Pure water (ion-exchanged water) 17 ml Sulfuric acid (50 w% aqueous solution) 3.0 g Aluminum sulfate (aqueous solution having an Al ₂ O ₃ conversion content of 8.1 w%) 20 g When using the fixing solution, the above composition A was added to 500 ml of water. , Composition B were melted in this order and finished to 1 l for use. The pH of this fixer 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%
R. H. Under the conditions described in (1), the emulsion side of the developed sample was rubbed with a rubber roller several times to bring tobacco ash close thereto, and whether or not it adhered to the film was examined 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 even at 10 cm or more ○ △ Practical trouble if above Absent.

(Surface resistivity measurement method) Using a teraohm meter VE-30 manufactured by Kawaguchi Electric Co., Ltd., applied voltage 100 V, 23
C, 20% R.C. H. It was measured under the conditions of.

(Haze test) After coating the multilayer photographic photosensitive layer,
The unexposure-developed sample was measured with a turbidimeter Model T-2600 DA manufactured by Tokyo Denshoku Co., Ltd., and haze was expressed in%.

Example 2 The conditions for preparing the sample were as follows.
Example 1 except that the undercoating coating solution B-4 was used in place of 3
The same evaluation as in Example 1 was performed.

<Undercoating Coating Liquid 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 (SnO ₂ / RhO ₂ -x = 1/1 (molar ratio)) 5 g Make up to 1 liter with water.

Example 3 The conditions for preparing the sample were as follows.
Example 1 except that subbing coating solution B-5 was used instead of No. 3
The same evaluation as in Example 1 was performed.

<Undercoating Liquid 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 (SnO ₂ / RhO _2-X = 1/1 (molar ratio)) 3 g Make up to 1 liter with water.

Comparative Example 1 The sample preparation conditions were as follows: undercoating coating solution B-
Example 1 except that the undercoating coating liquid B-0 was used in place of 3
The same evaluation as in Example 1 was performed.

<Undercoating Coating Liquid B-0> 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 l.

Comparative Example 2 The sample preparation conditions were as follows.
Example 1 except that the undercoating coating solution B-4 was used in place of 3
The same evaluation as in Example 1 was performed.

<Undercoating Coating Liquid 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 (Sb-doped SnO ₂ : navy blue) 15 g Water to make 1 liter.

Table 1 Volume fraction (%) Table Specific resistance ¹⁾ Dust adhesion test Coloring ²⁾ Example 1 26 2.5 * 10 ⁷ ○ Pass Example 2 8 1.8 * 10 ⁶ ○ Pass Example 3 5 1.2 * 10 ⁸ ○ △ Pass Comparative Example 1 0 9.5 * 10 ¹³ × Pass Comparative Example 2 26 1.2 * 10 ⁷ ○ Fail Note 1) Unit: Ω / □ Note 2) Coloring was judged visually. That is, a film which was visually recognized to be colored was rejected.

[0079]

As is apparent from Table 1, a photographic light-sensitive material having excellent transparency and having high antistatic performance even under low humidity could be provided. In addition, in Examples 1 to 3, generation of pressure fog and scratches was not observed, but it was observed in Comparative Examples 1 and 2.

Claims (2)

[Claims] 1. Ni, Ir, Rh, Nb, Ce, Zr,
A photographic light-sensitive material comprising at least one oxide containing at least one element selected from Th and Hf and having a volume resistivity of 10 ¹⁰ Ωcm or less. 2. Zn, Ti, Sn, In, Si, Mo,
2. The photographic light-sensitive material according to claim 1, containing at least one oxide containing at least one element selected from W and V.