JPS6398656A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain a silver halide photographic sensitive material having high antistatic property preventing falling off of the antistatic agent powder, generation of pressure fogging and abrasion defect by providing at least one layer contg. a fibrous electroconductive material consisting primarily of fibrous potassium titanate having the surface coated with an electroconductive material consisting primarily of metal oxide and compound oxide of metal. CONSTITUTION:At least one electroconductive layer contg. a fibrous electroconductive material dispersed in a binder is prepd. wherein said fibrous electroconductive material consists primarily of fibrous potassium titanate which is coated with a conductive material consisting primarily of at least one metal oxide selected from Zn, Ti, Sn, Al, In, Si, Mg, Ba, Mo, and W and/or compound oxide of said metals. The electroconductive material to be used for coating the fibrous potassium titanate is pref. crystalline metal oxide, particularly those having oxygen defect and contg. a small amt. of different atoms forming a donor for the metal oxide because of its high electroconductivity and advantageous characteristic of generating no fog in the silver halide emulsion. Preferred examples of the metal oxide are, particularly, Zn, TiO2 and SnO2.

Description

Detailed Description of the Invention (Industrial Field of Application) The present invention relates to a silver halide photographic material (hereinafter referred to as a photographic material) with improved antistatic properties.
In particular, the present invention relates to a photographic light-sensitive material with improved antistatic properties that do not adversely affect photographic properties and do not cause pressure blur or scratches.

(Prior Art) Photographic materials generally consist of an electrically insulating support and a photographic material layer, so during the manufacturing process and during use of the photographic material, contact with surfaces of the same or different materials may occur. Electrostatic charges are often accumulated during friction or peeling, and this accumulated electrostatic charge causes many problems. The most serious problem is that the photosensitive emulsion layer is sensitized by the discharge of accumulated electrostatic charges before processing, resulting in punctate spots or dendritic or feather-like streaks when the photographic film is processed. It is to produce. This is what is called a static mark, and it can significantly reduce the commercial value of the photographic film, or in some cases completely destroy it.For example, if this phenomenon appears on medical or industrial X-ray film, it can be extremely This phenomenon, which is easily recognized as leading to dangerous judgments, is one of the most troublesome problems as it becomes clear only after the image is developed. In addition, these accumulated electrostatic charges may cause secondary failures such as dust adhesion to the film surface or inability to apply uniformly.

Such electrostatic charges are often accumulated during the manufacture and use of photographic materials, as described above. For example, in the manufacturing process, it occurs due to contact friction between the photographic film and a roller, separation of the support surface and the emulsion surface during the winding and unwinding process of the photographic film, and the like. In finished products, the base surface and the emulsion surface are separated when the photographic film is wound and changed, or when the mechanical part of an automatic X-ray film camera or a fluorescent screen is separated. This occurs due to contact separation between the parts. It also occurs when there is contact with other packaging materials. Static marks on a photographic light-sensitive material induced by the electrostatic charge Mm become more noticeable as the sensitivity of the photographic light-sensitive material increases and the processing speed increases. Particularly in recent years, static marks have become more likely to occur due to increased sensitivity of photographic materials and increased exposure to harsh handling due to high-speed coating, high-speed photographing, high-speed automatic processing, etc.

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

Therefore, methods have been considered to improve the conductivity of supports and various coated surface layers of photographic materials, and attempts have been made to use various hygroscopic substances, water-soluble inorganic salts, certain surfactants, polymers, etc. It's here. For example, U.S. Patent No. 2.882.1
No. 57, No. 2,972.535, No. 3,062,78
No. 5, No. 3゜262.807, No. 3,514.291
3,615,531, 3,753,716, and 3,938.999, e.g.
．． No. 428,456, 3. 457゜076, same 3
, No. 454.625, No. 3,552.972, No. 3,
Surfactants such as those described in No. 655.387 are known.

However, many of these materials exhibit specificities depending on the type of film support and photographic composition, and while they may give good results for certain film supports and photographic emulsions and other photographic components, they may not work well for other photographic components. Film supports and photographic components not only are of no use in preventing static electricity, but may also have an adverse effect on photographic properties. More importantly, the electrical conductivity of these materials is dependent on humidity, and they lose their function as a conductive layer under low humidity conditions, which is a major drawback.

In addition, Japanese Patent Publication No. 35-6616 describes a technology using tin oxide as an antistatic treatment agent, but this technology uses amorphous tin oxide colloid, and its conductivity It is a material that has humidity dependence and loses its function as a conductive layer under low humidity, and is essentially no different from the various substances described above.

On the other hand, in JP-A No. 56-143431, crystalline metal oxides such as zinc oxide, stannic oxide, and indium oxide, whose conductivity hardly depends on humidity, are used as conductive materials for photographic light-sensitive materials. things are disclosed.

(Problems to be Solved by the Invention) However, when a layer containing such conductive metal fine particles is provided in contact with silver halide, pressure blots or scratches may occur on the image due to friction during handling. There was a problem that it was easy to occur. Furthermore, when mixed with a binder, fine particles present on the surface may fall off due to friction during the manufacturing process or handling.
In the manufacturing process, there was also the problem that it adhered to the rollers and damaged the products being transported.

Therefore, a first object of the present invention is to provide a photographic material with excellent antistatic properties.

A second object of the present invention is to provide a photographic material with excellent antistatic performance that does not cause dusting of the antistatic agent.

A third object of the present invention is to provide a photographic material that has excellent antistatic properties and does not cause pressure fog or scratches.

(Means for solving the problems) These aspects of the present invention include Zn, Tis SnsAl
, I n, S LSMg, BaSMo5 W, and/or at least one metal composite oxide composed of these metal oxides. This was achieved by a silver halide photographic light-sensitive material characterized in that the surface is coated with at least one layer containing a fibrous electrically conductive material whose main component is fibrous potassium titanate.

This solves the conventional problem by making the conductive metal oxide used in the present invention in the form of fibers, whereas the conductive metal oxides used in the past are in the form of fine particles. It is.

Next, the fibrous potassium titanate coated with the conductive material of the present invention will be described.

In the present invention, the conductive substance used to coat the fibrous potassium titanate is preferably a crystalline metal oxide, especially one containing oxygen defects and forming a donor for the metal oxide used. Those containing a small amount of foreign atoms are preferable because they have high conductivity (and do not fog the silver halide emulsion. Examples of gold M oxides include ZnO1T).
i02.5n02, Al1203, In2O3, SiO
2, MgO, BaO1M002, v2o5, etc., or composite oxides thereof are preferable, especially zno, 'ri02
and 5n02 are preferred. Examples involving different atoms include:
For example, for ZnO, additions such as Al % I n, for 5n02, additions of Sb, Nb, halogen elements, etc., and for TiO2, additions of Nb.

Addition of Ta or the like is effective. The amount of these foreign atoms added is preferably in the range of 0.01 mo1% to 30 mo1%, and particularly preferably in the range of 1 mo1% to 10 mo1%.

In addition, the volume resistivity of these conductive fine particles is 107Ω” (
It is preferable that it is less than 1Il cm, especially 105 Ω"cm.

In the present invention, potassium titanate is used as the base material for coating the conductive substance, which is 2O-nTi0.
It is a well-known compound represented by 2.mH2O (in the formula, n means a positive real number of 8 or less, and m means O or a positive real number of 4 or less), and is easily available as a commercial product. Particularly preferred is 20-6Ti02.mH2O.

The size of the fibrous potassium titanate as a base material used in the present invention is as follows: fiber length is 0.5 to 30 μm, diameter is 0.
．． The fiber length to diameter ratio (aspect ratio) is 3 to 500. Preferably used fibrous potassium titanate has a fiber length of 1 to 25 μm, a diameter of 0.05 to 1 μm, and an aspect ratio of 5 to 3.
00.

The fibrous potassium titanate coated with the conductive substance of the present invention can be obtained by coating the above-mentioned fibrous potassium titanate with the above-mentioned conductive substance. Here are some methods that have been used.

The size of the coated fibrous conductive potassium titanate is
It is approximately the same as the fibrous potassium titanate before coating, and has a fiber length of 1 to 25 μm, a diameter of 0,605 to 1 μm, and an aspect ratio of 5 to 300. The thickness of the conductive material to be coated is preferably in the range of about 1 to 1QQ nm; if the thickness is too thick, the aspect ratio will be affected, and if it is too thin, sufficient conductivity will not be obtained.

In the present invention, a small portion of the fibrous conductive material may be replaced with crystalline metal oxide particles as described in JP-A-56-143431. Further, the conductive layer of the present invention can contain a conductive polymer compound. These compounds include, for example, polyvinylbenzenesulfonic acid salts, polyvinylbenzyltrimethylammonium chloride, U.S. Pat.
, 137,217, polymer latexes described in US Pat. No. 4.070.189, 0L32830767, etc. are preferred.

The fibrous conductive substance and the conductive polymer compound are used after being dispersed or dissolved in a binder.

The tsuminder used in the present invention is not particularly limited as long as it has film-forming ability, but examples include proteins such as gelatin and casein, carboxymethyl cellulose, hydroxyethyl cellulose, acetyl cellulose, diacetyl cellulose, and triacetyl cellulose. cellulose compounds such as dextran, agar, sodium alginate, starch derivatives, polyvinyl alcohol, polyvinyl acetate, polyacrylic ester, polymethacrylic ester, polystyrene, polyacrylamide, poly-N-vinylpyrrolidone, polyester, Examples include synthetic polymers such as vinyl chloride and polyacrylic acid.

In particular, gelatin (lime-processed gelatin, acid-processed gelatin,
enzymatically decomposed gelatin, phthalated gelatin, acetylated gelatin, etc.), acetylcellulose, diacetylcellulose, triacetylcellulose, polyvinyl acetate, polyvinyl alcohol, polybutyl acrylate, polyacrylamide, dext in the conductive layer to lower the resistance. It is preferable that the volume content of the conductive substance in the layer is high, but in order to have sufficient strength as a layer, a binder of at least 5% is required, so the volume content of the fibrous conductive substance should be 5 to 5%. A range of 95% is desirable.

The amount of the fibrous conductive substance used is preferably 0.05 to 20 g, particularly 0.1 to 20 g per square meter of photographic material.
og is preferred. This not only provides good antistatic properties and prevents the fibrous conductive material from falling off, but also prevents the occurrence of pressure caps, scratches, etc. during handling of the photographic material.

In the present invention, at least one conductive layer containing a fibrous conductive substance is provided as a constituent layer of the photographic light-sensitive material. Two or more layers can be provided if necessary.

In the present invention, even better antistatic properties can be obtained by using a fluorine-containing surfactant in addition to the above-mentioned fibrous conductive material. The fluorine-containing surfactant added layer used in this case may be in any of the constituent layers of the photographic light-sensitive material, but it is preferably added to the protective layer, and especially added to the outermost layer. is preferred.

Preferred fluorine-containing surfactants that can be used in combination in the present invention include fluoro-alkyl groups having 4 or more carbon atoms;
It has an alkenyl group or an aryl group, and the ionic groups include anionic groups (sulfonic acid (salt), sulfuric acid (salt), carboxylic acid (salt), phosphoric acid (salt)), cationic group (amine salt, ammonium salt) , aromatic amine salts, sulfonium salts,
phosphonium salt), betaine group (carboxyamine salt,
Examples include activators having carboxyammonium salts, sulfoamine salts, sulfoammonium salts, phosphoammonium salts) or nonionic groups (substituted or unsubstituted polyoxyalkylene groups, polyglyceryl groups, or sorbitan residues).

These fluorine-containing surfactants are disclosed in JP-A-49-10722.
No., British Patent No. 1,330.356, Japanese Unexamined Patent Publication No. 1983-8
No. 4712, No. 54-14224, No. 50-1132
No. 21, U.S. Patent No. 4.335.201, U.S. Patent No. 4,34
No. 7,308, British Patent No. 1,417.915, Japanese Patent Publication No. 52-26687, No. 57-26719, British Patent No. 59
-38573, JP-A-55-149938, JP-A No. 54
-48520, 54-14224, 58-20
No. 235, No. 57-146248, No. 58-1965
No. 44, British Patent No. 11.439.402, etc.

The amount of fluorine-containing surfactant added is 0.0001 g.
/m2 to 2.0g/m2 is preferable, especially 0.0005
~0.4 g/m2 is preferred.

Next, preferred specific examples of the fluorine-containing surfactant in the present invention are described below.

I -I C8F 17 SO3K I-2C7Fx5COONa 1-3 C6F17CH2CH20SO3NaI-5 ■-8 ■-13 ■-14 ■-15 ■-16 ■-17 ■-22 I-23 ■-24 C7F15Coo(-CH2CH20U-H■ -27 Cl □ F21 Coo-(-CH2CH20 Yukimi H
■-29 ■-31 n+m-11,5 C6F t 7 CH2CH20-(-CH2CH20
KaH■-35? C9F17 ■-37 C9F 190 (-CH2CH20-)-CH3■-3
8 (?C9F17 ■-39 ■-40 ■-41 Examples of the support used in the present invention include cellulose nitrate film, cellulose acetate film, cellulose acetate butyrate film, cellulose acetate propionate film, polystyrene film, There are polyethylene terephthalate films, polycarbonate films, and other 8IW products thereof.More specifically, baryta or α-olefin polymers, especially polyethylene, polypropylene, ethylene-butene copolymers, etc., containing α-olefins having 2 to 10 carbon atoms. Examples include paper coated or laminated with a polymer.

These supports are appropriately selected from transparent and opaque supports depending on the intended use of the photographic material. Further, the transparent support is not limited to being colorless and transparent, but can also be colored and transparent by adding dyes and pigments.

In the present invention, another antistatic agent can also be used in the protective layer or other layers of the photographic material, and by doing so, a more preferable antistatic effect can be obtained. Such antistatic agents include, for example, U.S. Pat.
．． 882.157, 2,972.535, 3,
No. 062,785, No. 3,262,807, No. 3.
514. No. 291, No. 3,615.531, No. 3,
753゜716 No. 3,938,999, No. 4,07
No. 0゜189, No. 4,147.550, German Patent No. 2
．． 800.466, JP 48-91,165, JP 48-94.433, JP 49-46゜733, JP 5
No. 0-54.672, No. 50-94.053, No. 52
-129.520, etc.,
For example, U.S. Patent No. 2982.651, U.S. Pat.
．． No. 456, No. 3.457,076, No. 3,454.
No. 625, No. 3,552.972, No. 3,655,3
No. 87, JP-A-54-159223, JP-A No. 57-109
No. 947, No. 53-46022, No. 52-13062
No. 5, No. 59-57231, No. 52-55521,
No. 58-203435, No. 58-208743, No. 59-191034, British Patent No. 774.806,
Japanese Patent Application No. 61-16056, Japanese Patent Application No. 61-13398, Japanese Patent Application Publication No. 54-89626, Japanese Patent Application No. 55-70837,
No. 60-76741, No. 60-80848, No. 61
Surfactants such as those described in No.-41143, etc.
For example, U.S. Patent Nos. 3,062,700 and 3,245
．． Gold n oxide, colloidal silica, etc., barium strontium sulfate, polymethyl methacrylate, methyl methacrylate-methacrylic acid copolymer, colloidal silica or powder as described in No. 833, No. 3,525.621, etc. Examples include so-called matting agents made of silica and the like.

Also, ethylene glycol, propylene glycol) Lt,
1. 1. 1-) Limethylolbroban, etc., JP-A-1972
Polyol compounds such as those shown in No. 4-89626 can be added to the protective layer or other layers of the present invention,
By doing so, a more preferable antistatic effect can be obtained.

The photosensitive materials according to the present invention include ordinary black-and-white silver halide photosensitive materials (for example, black-and-white photosensitive materials for photography, black-and-white photosensitive materials for X-rays, black-and-white photosensitive materials for printing, etc.), and ordinary multilayer color photosensitive materials ( Examples include color reversal films, color negative films, color positive films, etc.) and various photosensitive materials. It is particularly effective for silver halide photosensitive materials for high-temperature rapid processing and high-sensitivity silver halide photosensitive materials.

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

Binders for the photographic layer include proteins such as gelatin and casein; cellulose compounds such as carboxymethyl cellulose, hydroxyethyl cellulose, and dextran; sugar derivatives such as agar, sodium alginate, and starch derivatives; synthetic hydrophilic colloids such as polyvinyl alcohol, poly-
N-vinylpyrrolidone, polyacrylic acid copolymer, polyacrylamide, or derivatives and partial hydrolysates thereof can also be used in combination.

Gelatin referred to herein refers to so-called lime-treated gelatin, acid-treated gelatin, and enzyme-treated gelatin.

In the photographic constituent layer of the present invention, known surfactants may be added alone or in combination.They are used as coating aids, but sometimes they are used for other purposes, such as emulsification and dispersion. It is also commonly used for sensitization and other improvements in photographic properties.

These surfactants include natural surfactants such as saponin, nonionic surfactants such as alkylene oxide, glycerin, and glycidol, higher alkylamines, quaternary ammonium salts, lysine and other heterocycles, and phosphonium. or cationic surfactants such as sulfoniums; anionic surfactants containing acidic groups such as carboxylic acids, sulfonic acids, phosphoric acids, sulfuric esters, and phosphoric esters; sulfuric or phosphoric acids of amino acids, aminosulfonic acids, and amino alcohols; It is divided into amphoteric surfactants such as esters.

In addition, in the present invention, lubricating compositions such as U.S. Pat. No. 3,079.837, U.S. Pat. 294.537
Modified silicones such as those shown in Japanese Patent Laid-Open No. 52-1295-20 can be included in the photographic constituent layer.

The photographic light-sensitive material of the present invention contains the polymer latex described in U.S. Pat. No. 3,411,911, U.S. Pat.
can be included.

In addition, the photographic light-sensitive material of the present invention contains an alkyl acrylate latex described in U.S. Pat. No. 3,411,911, U.S. Pat. can be included.

The silver halide grains in the emulsion may have a regular crystal shape such as a cube or an octahedron, or may have an irregular crystal shape such as a spherical shape, a plate shape, a potato shape, etc.
It may have an irregular crystal form or a composite form of these crystal forms.It may consist of a mixture of particles of various crystal forms, and it may have a tabular shape with a particle diameter of 5 times or more the particle thickness. The particles are preferably used for the present invention (in detail, RH5EARC
O5URE Volume 225 Item 22534 P, 2
0-P.

58. January issue, 1983, and JP-A-58-1279
No. 21 and No. 58-113926).

In the present invention, the photosensitive silver halide emulsion may be a mixture of two or more types of silver halide emulsions, the emulsions to be mixed may differ in grain size, halogen composition, sensitivity, etc.; The emulsion may be mixed with a substantially non-photosensitive emulsion (which may or may not be covered on the surface or inside), or may be separated into separate layers.

For example, in the same layer as a spherical or potato-shaped photosensitive emulsion and a photosensitive silver halide emulsion consisting of tabular grains with a grain size of 5 times or more the grain thickness, or in JP-A-58-127
As described in Japanese Patent No. 921, it may be used in different layers. 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 vice versa. It may be on the far side.

The photographic emulsion used in the present invention is B. gelafchides (
Chimie et Phys Photography (Chimie et Phys Photography) by P. Glafkides
iquephotographique) J (Paul Montel, published by Paul Monte1, 196
7 years), G.F. Duffi
Photographic Emulsion Chemistry (Photographic Emulsion Ch.
emistry ) J (The Focal Press
The Focal Press, 1966), V. L. Zelikman et al.
Making and Coating Photographic Emulsions (Making a
nd Coating Photographic E
+aulsion) J (Focal Press T
It can be adjusted using the method described in HeFocal Press, 1964).

The silver halide emulsion and other hydrophilic colloid layers in the photographic light-sensitive material of the present invention can be hardened with various organic or inorganic hardening agents (II alone or in combination). Typical examples include mucochloric acid, formaldehyde, Trimethylolmelamine, glyoxal, 2,3-dihydroxy-1,4-dioxane, 2,3-dihydroxy-
Aldehyde compounds such as 5-methyl-1,4-dioxane, succinic aldehyde, and glutaraldehyde; divinyl sulfone, methylene bismaleimide, 1°3.5-
triacryloyl-hexahydro-S-triazine,
1.3.5-)rivinylsulfonyl-t-sahyl'
Active vinyl compounds such as rho-3-triazine bis(vinylsulfonylmethyl)ether, 1,3-bis(vinylsulfonylmethyl)propanol-2, bis(α-vinylsulfonylacetamido)ethane; 2,4-dichloro-6 -hydroxy-3-triazine sodium salt,
Active halogen compounds such as 2.4-dichloro-6-nodoxy-S-triazine; 2.4.6-) ethyleneimine compounds such as diethyleneimino-3-triazine; and the like.

Types of silver halide used in the silver halide emulsion layer, surface protective layer, etc. of the photographic light-sensitive material of the present invention, manufacturing method, chemical sensitization method, antifoggants, stabilizers, hardeners, plasticizers, lubricating oils, Coating aids, matting agents, brighteners, spectral sensitizing dyes, dyes,
There are no particular restrictions on color couplers etc. For example, Research Disclosure magazine (Research D
isclosure) Volume 176, pages 22-31 (197
You can refer to the description in December 2010).

The present invention will be illustrated below with reference to Examples, but the present invention is not limited thereto.

Example 1 An intermediate layer, an emulsion layer, and a protective layer were provided in this order on one side of a subbed polyethylene terephthalate film support (approximately 175μ) (emulsion side), and a back layer (back side) was provided on the other side. A protective layer of a photographic material having the structure and/or
Alternatively, Samples 1-1 to 1-9 in which the intermediate layer contained a conductive material and a fluorine-containing surfactant as shown in Table 1 were prepared by applying and drying according to a conventional method. The composition of each layer is as follows.

A) Emulsion layer side (a) Intermediate layer binder: gelatin 0.4 g/m2 Hardener = 1.3-bis(vinylsulfonyl)-propanol-2 1.2 g/100 g gelatin (b) Emulsion layer binder: gelatin 2.5g/m2 Coated silver amount: 5g/m2 Silver halide composition: Agl 1.5mo1% and AgBr98
．． 5mo1% Fog inhibitor: 1-phenyl-5-mercaptotetrazole 0.5g/Ag100g Hardener: 1.3-bis(vinylsulfonyl)-propanol-2 1.2g/100g gelatin (c) Protective layer binder: Gelatin 0.3g/m2 Coating agent: Sodium pt-octylphenoxyethoxyethanesulfonate 10mg/m2 Hard [$1: 1.3-bis(vinylsulfonyl)-propanol-2 1.2g/100g gelatin B) Back side back layer binder: Gelatin 1.7g/m2 Coating agent: N-oleyl sodium N-methyltaurate
7 mg/m2 Hardener: 1
, 3-bis(vinylsulfonyl)-propanol-2 1.2 g/100 g gelatin (1) Static mark test After conditioning the unexposed sample in a dark room at 25°C and 10% RH for 2 hours, the same air conditioning was performed. In a dark room, the sample was rubbed with a rubber roller and a urethane roller to see how the static mark would form on various materials, then developed with the following developer, fixed, and washed with water. The occurrence of static marks was investigated.

(Developer composition) Warm water 800ml Sodium tetrapolyphosphate 2.0g Anhydrous sodium sulfite 50g Hydroquinone 10g Sodium carbonate (1
water salt) 40g 1-phenyl-3-pyrazolidone 0.3g potassium bromide
Add 2.0g water
1000mj! (pH 10, 2) The antistatic properties of these samples are shown in Table 2.

In Table 2, the degree of static mark occurrence was evaluated in the following four stages.

A: No static marks were observed at all.

B: Slightly acceptable.

C: Quite acceptable.

D: Appeared almost entirely.

(2) Powder drop test After cutting the sample into 3.5 cm x 30 cm and conditioning the humidity at 25°C and 60% relative humidity for 3 hours, place a 3 cm x 3 cm piece of white drawing paper with a 3 kg load on the emulsion layer side of the sample and move it back and forth 3 times. I rubbed it.

The deposits on the drawing paper were evaluated on the following four scales.

A: All deposits (not observed).

B: Slightly acceptable.

C: Quite acceptable.

D: It is observed almost all over the surface.

(3) Relative Sensitivity The sample was exposed to tungsten lamp light through a Fuji Film filter 5P-14, and then processed according to the development method described above.

The sensitivity of Sample 1-1 (control) was set at 100 and other samples were evaluated.

(4) Scratch test 0 to 20 on a 1cm Scotch nylon scrubber
A load of 0 g was applied, the sample was placed on the emulsion layer side surface of the unexposed sample in a dark room, and the sample was pulled at a speed of 5 mm/sec. Thereafter, development processing was performed immediately. The load at which scratches (black lines) were visible on the developed film was used as a measure of the likelihood of scratches. The higher the load, the less likely it is to get scratched.

(5) Pressure capri test Wrap the surface of a 3x3cm square piece of wood with gauze, 0°39kg
/cm2 was applied and pulled at a speed of 5 mm/sec over the surface of an unexposed sample placed in a dark room. After that, develop it in the same way as in the scratch test, and record the density of the pressure capri part with a self-recording density needle (manufactured by Fuji Photo Film Jun).
The pressure capri was determined by subtracting the capri density of the area where no pressure was applied.

As is clear from Table 1 (C) Control Table 2 (c) Control Table 2, the samples of the present invention (1-2 to 1
-5) has excellent antistatic performance with almost no static marks observed on rollers made of two materials (rubber and urethane) with different charge series under a humidity condition of 10% relative humidity. Not only does it have powder,
Sensitivity, scratches, and pressure capri are all good. On the other hand, the control without a conductive layer has significantly inferior antistatic properties. Among comparative samples using conductive metal fine particles, Samples 1-6 and 1-7, in which the fine particles were used in the protective layer, showed almost no static marks, but had problems with powder stains, sensitivity, scratches, and pressure caps. is inferior. Sample 1-8.1-9 in which the fine particles were used in the intermediate layer had improved antistatic properties but was inferior in sensitivity, scratches, and pressure capri.

As is clear from this example, the present invention made it possible to obtain a good photographic material with greatly improved antistatic properties.

Claims (1)

[Claims] Zn, Ti, Sn, Al, In, Si, Mg, Ba, M
A fibrous material whose surface is coated with a conductive material mainly consisting of at least one metal oxide selected from o, W, and/or at least one metal composite oxide composed of these metal oxides. A silver halide photographic material comprising at least one conductive layer in which a fibrous conductive material containing potassium titanate as a main component is dispersed in a binder.