JPH0120736B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention has improved adhesion to a silver halide photographic layer (hereinafter referred to as photographic layer) applied later,
At the same time, the present invention relates to a photographic support in which the charging characteristics of the support are improved. One of the characteristics required of a photographic support is strong adhesion to a subsequently applied photographic layer, and the other is charging characteristics of the support. Photographic supports generally have electrical insulating properties, and electrostatic charges are removed by contact friction or peeling between surfaces of the same or different materials during the manufacturing process of photographic light-sensitive materials and during use. Often accumulated. This accumulated electrostatic charge causes many problems, but the most important problem is the damage to the support film that occurs between the support film and the transport roller during the process of coating the support with photographic emulsion. Static electricity is discharged near the photographic emulsion coating head, and the light generated at that time causes dot-like, dendritic, or feather-like streaks to appear on the emulsion layer. This is what is called a static mark, and it significantly impairs the commercial value of photographic film, and in some cases causes it to disappear completely. For example, if it appears in medical or industrial X-ray film, it will be easily recognized that it will lead to a very dangerous judgment. This phenomenon becomes apparent only after development, and is one of the most troublesome problems. Further, these accumulated electrostatic charges may cause secondary failures such as dust adhesion to the film surface or uneven coating. Various methods have been tried in the past for firmly adhering the photographic layer onto the first photographic support. The method is () to directly apply a photographic layer after electron impact treatment such as discharge treatment or ultraviolet treatment; () to apply an undercoat layer after electron impact treatment, and then Method for coating photographic layers () After performing electron impact treatment, a first undercoat layer is applied, a second undercoat layer made of a hydrophilic polymer is further applied, and a photographic layer is applied on top of this. There is a method of painting. These methods are described, for example, in U.S. Pat.
No. 2698241, No. 2764520, No. 2864755, No. 2864756, No. 3475193, British Patent No. 788365
No. 804005 and No. 891469. Among these methods, the methods () and () above are generally widely used. Although method () is more advantageous than method () in terms of adhesion, it has the disadvantage of increasing process costs because it requires two undercoat layers. Therefore, various attempts have been made to obtain sufficient adhesive strength using the method (). For example, JP-A-50-151135 and JP-A-50-
No. 110,323 discloses a method in which a subbing layer contains droplets of a droplet solid solution having a diameter smaller than the thickness of the layer. However, according to facts known in the art, this method requires a dispersion step to disperse the droplets, and the droplets thus dispersed often aggregate, resulting in changes in the diameter distribution of the droplets. Changes occur easily, and it takes a great deal of effort to continue producing an undercoat layer of the same quality over a long period of time. Additionally, attempts have been made to apply a corona treatment to the undercoat layer after applying it, as described in U.S. Pat. , requiring new capital investment. Another method is to add inorganic particles as an adhesion promoter to a polymer undercoat layer in an amount of 5 to 80% by weight based on the weight of the polymer or copolymer, as described in JP-A-54-70029. There is a way to make it exist. In the case of the above-mentioned patent, it does have an effect of promoting adhesion, but the amount added is too small to obtain conductivity of the support.
For example, when inorganic particles with a specific gravity of 5 are added in an amount of 80% by weight based on the weight, the volume fraction of the inorganic particles in the undercoat layer is about 14%. Moreover, the best way to eliminate the above-mentioned electrostatic disturbance is to increase the electrical conductivity of the material so that the electrostatic charge can be dissipated in a short period of time before the accumulated charge is discharged. Various efforts have been made in the past to provide supports with such electrically conductive layers. For example, there is a method of providing a deposited layer of metal oxide, as described in US Pat. No. 3,864,132. However, when this method is applied to the photographic industry, it requires capital investment in vapor deposition equipment, and the vapor deposition processing speed is generally slower than the coating processing speed used in the photographic industry, so it must be considered a method with low productivity. As a method to overcome this drawback, there is a method using a conductive water-dispersible polymer and a crosslinkable latex, as described in JP-A-55-145783, for example. However, since this method uses hydrophilic latex, when this layer is used as an undercoat layer, the undercoat layers may be mixed together or There is a risk that unnecessary adhesion will occur between the layer and the opposite surface of the support, making it impossible for the lower drag roll to unwind. Furthermore, when the conductive latex is a cationic latex, when used in an undercoat layer, it may have an adverse effect on the photographic properties peculiar to cationic materials. On the other hand, for example, U.S. Patent No. 3062700,
-113224 and No. 55-12927, etc., crystalline metal oxides such as zinc oxide, stannic oxide, and indium oxide are used as conductive materials for conductive supports of electrophotographic photoreceptors or electrostatic recording materials. It is known to use However, the use of these crystalline metal oxide particles as antistatic agents in silver halide emulsions is completely unknown, and furthermore, it is unclear how these conductive materials interact with the silver halide photosensitive emulsion layer. It was completely unpredictable whether it would last or not. By the way, silver halide,
Copper halides are used, but as shown in U.S. Pat. No. 3,428,451, it has been clearly shown that these conductive materials interact with silver halide emulsion layers and have an adverse effect on photographic properties. There is. Furthermore, images obtained using photographic light-sensitive materials may be observed using transmitted light or reflected light. In the latter case, it is preferable that the reflectance of the non-image area be as high as possible. On the other hand, in the former case, it is preferable to increase the light transmittance of the area without an image, and it is desirable to reduce light scattering by the photographic light-sensitive material.
In order to reduce light scattering as much as possible, there are major restrictions when introducing a conductive layer into a photographic light-sensitive material to prevent static electricity. However, it was necessary to use conductive water-dispersible polymers, etc., which have unnecessary adhesive properties. Thus, the aforementioned U.S. Pat. No. 3,062,700;
From this point of view, the zinc oxide, conductive tin oxide, and indium oxide described in JP-A-52-113224 and JP-A-55-12927 are useful for conductive paper for electrophotography or electrostatic recording. Although it can be used, it cannot be used as is for silver halide photographic materials in which images are observed using transmitted light. A primary object of the present invention is to provide a support with improved adhesion to photographic layers. A second object of the present invention is to improve charging characteristics,
It is an object of the present invention to provide a support which can be uniformly coated with less concern about the generation of static marks or the adhesion of dust to the film surface during an emulsion coating process. A third object of the present invention is to provide a method for improving the charging characteristics of a support without impairing the photographic characteristics. A fourth object of the present invention is to provide a photographic material that satisfies the above three objects and is suitable for observing images using transmitted light. These objects of the invention are such that after electron bombardment treatment is applied to at least one side of the photographic support material, ZnO, TiO ₂ , SnO ₂ , Al ₂ O ₃ , In ₂ O ₃ , MgO,
Fine particles containing at least one kind of crystalline metal oxide selected from BaO and _MoO3 , or composite oxides thereof, or a small amount of foreign atoms therein, and the volume resistivity of the fine particles is 10 ⁷ A photographic support having improved charging characteristics and adhesion of a photographic layer, characterized in that a layer containing fine particles of Ω-cm or less, a hydrophilic binder, and a curing agent for the hydrophilic binder is coated on the support. It is achieved by doing so. Preferred conductive particles used in the present invention are crystalline metal oxide particles, but those containing oxygen defects and those containing a small amount of foreign atoms that form donors for the metal oxide used are Generally speaking, the latter is preferred because of its high conductivity, and the latter is particularly preferred because it does not cause fog to the silver halide emulsion. Examples of metal oxides are ZnO,
_TiO2 , _SnO2 , _Al2O3 , _In2O3 , _MgO , _BaO ,
MoO ₃ etc. or composite oxides of these are good,
Particularly preferred are ZnO, _TiO2 and _SnO2 . Examples containing different atoms include ZnO, Al, In, etc., and TiO ₂
Nb, Ta, etc. for SnO ₂ , Sb,
Examples include Nb and halogen elements. The amount of foreign atoms added is preferably in the range of 0.01 to 30 mol%, but 0.1 to 30 mol%.
Particularly preferred is 10 mol%. The particle size of the crystalline metal oxide particles used in the present invention is preferably small in order to minimize light scattering, but should be determined using the ratio of the refractive index of the particles and the binder as a parameter. Using Mie's theory, 550n by the way
For light with a wavelength of m, the scattering efficiency is 5, 10, 30, 50
Table 1 shows the particle size corresponding to %. Although a table similar to Table 1 can be made for each wavelength, it is omitted here and Table 1 is used as a guide for light scattering for white light.

[Table] Among photographic materials, it is preferable that the scattering efficiency of the highlight part of the image be 50% or less for the type of photosensitive material such as X-ray film, in which the image can be directly observed with the naked eye, and the color slide , color negative film, black and white negative film, motion picture film, etc., in which images are projected and used, the scattering efficiency in highlight areas is preferably 20% or less. Although it is not necessary for light scattering to be small in color prints, black and white photographic paper, etc., it is obvious that there is no problem in applying the present invention to these. Table 2 shows the refractive index of metal oxides that are the base materials of the main conductive particles used in the present invention. Table 2 ZnO 2.0 TiO ₂ 2.7-2.9 SnO ₂ 2.0 Al ₂ O ₃ 1.7-1.8 The binder used in the present invention will be described later, and its refractive index is approximately in the range of 1.4-1.6.
Therefore, judging from the values in Table 1, approximately
Most of the present invention can be achieved by using conductive particles of 0.5μ or less, and a sensitive material with extremely high light transmittance with a light scattering efficiency of 10% or less can be obtained by using conductive particles of 0.2μ or less. It is possible. The conductive layer used in the present invention is at 25℃ and 25%RH.
Even in such low humidity conditions, the surface resistivity is 10 ¹¹ Ω.
Below, it is desirable to set it preferably to 10 ⁹ Ω or less. For this purpose, it is used as a regular undercoat layer.
Assuming a coating thickness of about 0.1 to 1 μm, the volume resistivity of the conductive particles is 10 ⁷ Ω-cm or less, preferably 10 ⁵
It is desirable that it be Ω-cm or less. The conductive fine particles made of crystalline metal oxide used in the present invention are mainly produced by the following method. The first method is to prepare metal oxide fine particles by firing and then heat-treat the metal oxide particles in the presence of a different type of atom to improve conductivity.The second method is to prepare metal oxide fine particles by firing and heat-treating the metal oxide fine particles in the presence of a different type of atom to improve conductivity. A third method is to allow atoms to coexist, and a third method is to lower the oxygen concentration in the atmosphere to introduce oxygen defects when producing metal fine particles by firing. In the first method, the conductivity of the surface of the fine particles can be effectively improved, but since particle growth may occur during the heat treatment, it is necessary to select the conditions. Further, it may be better to perform the heat treatment in a reducing atmosphere. The second method is preferred because it appears to require the least manufacturing expense. For example, in a method to obtain SnO ₂ fine particles by spraying β-stannic acid colloid (amorphous), which is a hydrate of SnO ₂ , into a firing furnace, antimony chloride, antimony nitrate, and antimony oxide are added to the β-stannic acid colloid. Conductive SnO ₂ fine particles can be obtained by allowing a hydrate, etc. of SnO 2 to coexist. As another example, in the so-called gas phase method in which SnCl ₄ and TiCl ₄ are oxidatively decomposed to produce SnO ₂ and TiO ₂ , conductive SnO ₂ and TiO ₂ can be produced by coexisting salts of different atoms during oxidative decomposition. Obtainable. Furthermore, in the method of thermally decomposing an organic acid salt of a metal to obtain a metal oxide, there is also a method in which salts of different metals are allowed to coexist during the thermal decomposition. As an example of the third method, in the vacuum evaporation method in which metal oxide particles are obtained by evaporating metal in an oxygen atmosphere, there is a method in which the amount of oxygen is slightly insufficient, or a method in which metal oxide particles are obtained by evaporating metal in an oxygen atmosphere. There is a method of heating metal salts. Although it is desirable that the conductive particles used in the present invention be as small as possible, the fine particles obtained by the above-mentioned particle preparation method may be strongly aggregated and become coarse particles. To avoid this, when producing conductive particles, it is often effective to coexist fine particles that do not directly contribute to improving conductivity as a micronization aid. Particles used for this purpose include fine metal oxide particles that are not made for the purpose of increasing conductivity (e.g. ZnO, TiO ₂ , Al ₂ O ₃ , SiO ₂ , MgO, BaO,
_WO3 , _MoO3 , _{P2O5 ,} etc.), _BaSO4 , _SrSO4 ,
Fine particles of sulfate such as CaSO ₄ , MgSO ₄ , etc.
There are fine particles of carbonates such as MgCO ₃ and CaCO ₃ . Since the particles mentioned here have little coloring, they can also be used by being dispersed in a binder together with conductive fine particles. In addition, physical or chemical treatment can be performed to remove most of the auxiliary particles and coarse particles. That is, a method in which the obtained particles are poured into a liquid, pulverized with a ball mill, sand mill, etc., and then ultrafine conductive particles are selectively collected by filtration, elutriation, centrifugal sedimentation, etc., or as described above. After crushing
An effective method is to dissolve only the auxiliary particles. It goes without saying that ultrafine conductive particles can be obtained even more effectively by repeating or combining these operations. Ultrafine conductive particles can be obtained more effectively by adding a surfactant as a dispersion aid, a small amount of binders that can be used in the present invention, or a small amount of Lewis acid or Lewis base to the liquid in which the particles are dispersed. . It is obvious that if chemical treatment is used in combination, the range of particles that can be used as auxiliary particles will be wider. Binders for the conductive layer used in the present invention include proteins such as gelatin, derivative gelatin, colloidal albumin, and casein; cellulose compounds such as carboxymethyl cellulose, hydroxyethyl cellulose, diacetyl cellulose, and triacetyl cellulose; agar, sodium alginate, and starch derivatives. sugar derivatives such as synthetic hydrophilic colloids such as polyvinyl alcohol, polyacrylic acid copolymers, or derivatives thereof, partial hydrolysates, vinyl polymers such as polyacrylic esters and their copolymers, rosin, silica, etc. Natural products and their derivatives, as well as many other synthetic resins, are used. Also used are water emulsions such as styrene-butadiene copolymer, polyacrylic acid, polyacrylic ester and its derivatives, polyvinyl acetate, vinyl acetate-acrylic ester copolymer, polyolefin, olefin-vinyl acetate copolymer, etc. can do. Among these, gelatin is most preferred. Alternatively, it is also possible to use colloids of hydrates of metal oxides such as aluminum oxide, tin oxide, vanadium oxide, etc. as the binder. In the undercoat layer used in the present invention, a conventionally known conductive polymer can be used as part or all of the binder. These compounds are
For example, polyvinylbenzenesulfonic acid salts, polyvinylbenzyltrimethylammonium chloride, U.S. Pat.
These include quaternary salt polymers described in US Pat. No. 4,126,467 and US Pat. No. 4,137,217, and crosslinked polymer latexes described in US Pat. In the present invention, a layer consisting of conductive inorganic metal oxide particles, a hydrophilic binder, and a crosslinking agent for the hydrophilic binder is provided in the undercoat layer of a photographic support. In order to reduce the amount, the following points should be kept in mind. In other words, light scattering occurs not only inside the undercoat layer;
This also occurs at the interface where the undercoat layer is in contact with other substances. In this case, since the binder for the undercoat layer and the binder for the photosensitive emulsion layer have approximately the same refractive index, the influence of light scattering at the interface between the two layers is not so large. On the other hand, when the undercoat layer is placed on the back side of the photosensitive material, that is, at a position where the photographic photosensitive material is in contact with an external medium (usually air), light scattering occurs at the interface between the undercoat layer and the medium. In order to suppress this light scattering, there is a method of providing a covering layer to cover the conductive layer.
This coating layer is one of the preferred embodiments of the present invention because it can also function as a protective layer for the undercoat layer. The thickness of the undercoat layer is usually about 0.05 to 3 .mu.m, and the particle diameter of the inorganic oxide particles is preferably about 0.01 to 1 .mu.m, more preferably about 0.05 to 0.5 .mu.m. If the particles are larger than this, the particles will not fit into the undercoat layer, and light scattering will be somewhat large. In order to use conductive particles more effectively and lower the resistance of the undercoat layer, it is better to have a high volume content of conductive particles in the undercoat layer. and the strength of the undercoat layer becomes weaker, so the volume content of conductive particles is 20~95%
More preferably 30-80%, still more preferably 40-70
A range of % is desirable. As the crosslinking agent for the hydrophilic binder used in the present invention, organic or inorganic crosslinking agents can be added alone or in combination. Examples of crosslinking agents include CEKMees and TH
The Theory of the Photographic by James
3rd edition (1966) U.S. Patent No. 3316095
No. 3232764, No. 3288775, No. 2732303,
Same No. 3635718, No. 3232763, No. 2732316, Same No.
No. 2586168, No. 3103437, No. 3017280, No.
No. 2983611, No. 2725294, No. 2725295, No.
No. 3100704, No. 3091537, No. 3321313, No.
No. 3543292, No. 3125449, British Patent No. 994869, No.
Curing agents described in No. 1167207 and the like are suitable. Typical examples include mucochloric acid, mucobromic acid, mucophenoxychloric acid, mucophenoxybromic acid, formaldehyde, dimethylol urea, trimethylolmelamine, glyoxal,
Aldehyde compounds and derivatives thereof such as monomethylglyoxal, 2,3-dihydroxy-1,4-dioxane, 2,3-dihydroxy-5-methyl-1,4-dioxane succinic aldehyde, 2,5-dimethoxytetrahydrofuran, and glutaraldehyde ; Divinyl sulfone N,
N'-ethylenebis(vinylsulfonylacetamide), 1,3-bis(vinylsulfonyl)-2-propanol, methylenebismaleimide, 5-acetyl-1,3-diacryloyl-hexahydro-
s-triazine, 1,3,5-triacryloyl-hexahydro-s-triazine, 1,3,5-
Active vinyl compounds such as trivinylsulfonyl-hexahydro-s-triazine; 2,4-dichloro-6-hydroxy-s-triazine sodium salt, 2,4-dichloro-6-methoxy-s-triazine, 2,4- dichloro-6-(4-sulfoanilino)-s-triazine sodium salt, 2,
4-dichloro-6-(2-sulfoethylamino)-
Active halogen compounds such as s-triazine, N,N'-bis(2-chloroethylcarbamyl)piperazine; bis(2,3-epoxypropyl)methylpropylammonium p-toluenesulfonate, 1,4- Bis(2',3'-epoxypropyloxy)butane, 1,3,5-triglycidyl isocyanurate, 1,3-diglycidyl-5-
Epoxy compounds such as (γ-acetoxy-β-oxypropyl) isocyanurate; 2,4,6
-Ethyleneimine compounds such as triethylene-s-triazine, 1,6-hexamethylene-N,N'-bisethyleneurea, and bis-β-ethyleneiminoethylthioether; 1,2-di(methanesulfonoxy)ethane , 1,4-di(methanesulfonoxy)butane, methane sulfonic acid ester compounds such as 1,5-di(methanesulfonoxy)pentane; dicyclohexylcarbodiimide, 1-dichlorohexyl-3-(3-trimethylaminopropyl)carbodiimide -Carbodiimide compounds such as p-toluenesulfonate, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride; 2,5-dimethylisoxazole perchlorate, 2-ethyl-5-phenyl isoxazole-3'-sulfonate, 5,
Isoxazole compounds such as 5′-(paraphenylene)bisisoxazole; chromium alum,
Inorganic compounds such as chromium acetate; N-carboethoxy-2-isopropoxy-1,2-dihydroquinoline, N-(1-morpholinocarboxy)-4-
Dehydration condensation type peptide reagents such as methylpyridium chloride; active ester compounds such as N,N'-adipoyldioxydisuccinimide and N,N'-terephthaloyldioxydisuccinimide;
Toluene-2,4-diisocyanate, 1,6-
Isocyanates such as hexamethylene diisocyanate; epichlorohydrin compounds such as polyamide-polyamine-epichlorohydrin reaction products; and the like. Preferred compounds include, for example, Japanese Patent Publication No. 48-
25402, and epoxy compounds such as 1,3,5-triglycidyl isocyanurate and , 2,4-dichloro-6-hydroxy-s-triazine sodium salt, and isocyanates such as 1,6-hexamethylene diisocyanate. Particularly preferred are epichlorohydrin compounds and epoxy compounds. The amount of crosslinking agent added is 0.01 to 50 mmole, more preferably 1 to 10 mmole per 100 g of hydrophilic polymer.
It's a mole. If the amount added is small, the wet adhesion of the film after coating the photographic layer will be weak, and if the amount added is large, it will cause various adverse effects on the photographic layer (e.g. Dm
(decreased). Further, the electron impact treatment used as a pretreatment in the present invention includes, for example, corona discharge treatment, glow discharge treatment, electrodeless plasma discharge treatment, ultraviolet irradiation treatment, and the like. Particularly preferred treatments are corona discharge treatment and glow discharge treatment. However, it goes without saying that the above range varies depending on the type of photographic film base used, the photograph, the composition, the form, or the coating method. Examples of the support used in the photographic material of the present invention include linear films such as cellulose nitrate film, cellulose acetate film, cellulose acetate butyrate film, cellulose acetate propionate film, polystyrene film, and polyethylene terephthalate film. Polyester (terephthalic acid, isophthalic acid, phthalic acid, 2,5-, 2,6- and 2,7-naphthalenedicarboxylic acid, succinic acid,
Sebacic acid, adipic acid, azelaic acid, diphenyldicarboxylic acid, hexahydroterephthalic acid,
or one or more dicarboxylic acids or lower alkyl diesters thereof, such as bis-p-carboxylphenoxyethane, optionally in combination with a monocarboxylic acid such as piparic acid, to combine one or more glycols, e.g. Ethylene glycol, 1,3-propanediol, 1,4
-obtained by condensation with heptanediol, neopentyl glycol or 1,4-cyclohexanedimethanol. ) polycarbonate film and other laminates thereof. More specifically, paper coated or laminated with baryta or α-olefin polymers, particularly polymers of α-olefins having 2 to 10 carbon atoms, such as polyethylene, polypropylene, ethylene-butene copolymers;
can be mentioned. These supports are selected from transparent ones and opaque ones depending on the intended use of the photosensitive material. Furthermore, even when the material is transparent, it is possible not only to make it colorless and transparent, but also to make it colored and transparent by adding dyes and pigments. The coating liquid for undercoating according to the present invention can be applied by a generally well-known coating method, such as a dip coating method, an air knife coating method, a curtain coating method, a roller coating method, a wire barcoding method, a gravure coating method, or the U.S. Pat. It can be coated by the extrusion coating method using a hopper as described in No. 2681294. U.S. Patent No. 2761791, U.S. Patent No. 3508947, U.S. Pat.
Two or more layers can be coated simultaneously by the method described in No. 2941898, No. 3526528, Ozaki et al., "Coating Engineering", p. 253 (published by Asakura Shoten, 1973). The coating amount of the subbing liquid according to the present invention is 0.01 to 10 c.c. per square meter of support in terms of solid volume.
It is preferably 0.1 to 3 c.c. The undercoating liquid thus applied is then dried in a drying process, but the conditions are 120°C to 200°C.
The heating time is from 10 seconds to 10 minutes, but the temperature and time can be appropriately determined within this range. If necessary, a surfactant, a swelling agent, a matting agent, and an antistatic agent may be added to the undercoat layer according to the present invention. Although it is not necessary to add a swelling agent, for example, phenol, resorcinol, etc. may be added.
The amount added is 1 to 10 g per subbing liquid. As the matting agent, silicon dioxide (silica), polystyrene, and polymethyl methacrylate having a particle size of 0.1 to 10 μm are preferable. As the antistatic agent, anionic or cationic surfactants, ionene polymers, maleic acid copolymers described in JP-A-49-3972, etc. can be used. In the photographic material of the present invention, each photographic constituent layer may also contain the following binder.
Examples of hydrophilic colloids include proteins such as gelatin, colloidal albumin, and casein; cellulose compounds such as carboxymethyl cellulose and hydroxyethyl cellulose; sugar derivatives such as agar, sodium alginate, and starch derivatives; synthetic hydrophilic colloids such as polyvinyl alcohol and poly-N-
Examples include vinylpyrrolidone, polyacrylic acid copolymer, polyacrylamide, or derivatives and partial hydrolysates thereof. Mixtures of two or more of these colloids are used if necessary. Among these, gelatin is the most used, and gelatin here refers to so-called lime-treated gelatin, acid-treated gelatin, and oxygen-treated gelatin. In addition to replacing part or all of gelatin with synthetic polymeric substances, so-called gelatin derivatives, i.e., functional groups contained in the molecule such as amino, imino, hydroxy, or carboxyl groups, can be replaced with groups that can react with them. It may be replaced with a reagent treated or modified with a single reagent, or a graft polymer in which molecular chains of a polymeric substance are bonded. The silver halide emulsion of the photographic light-sensitive material used in the present invention is usually prepared by combining a water-soluble silver salt (for example, silver nitrate) solution and a water-soluble halide salt (for example, potassium bromide) solution in the presence of a water-soluble polymer solution such as gelatin. It is made by mixing. As the silver halide, in addition to silver chloride and silver bromide, mixed silver halides such as silver chlorobromide, silver iodobromide, silver chloroiodobromide, etc. can be used. These silver halide grains are produced according to known and commonly used methods. Of course, it is also useful to use the so-called single jet method, double jet method, controlled double jet method, etc. These photographic emulsions are THJames and CEK
Mess, The Theory of the Photographic
Process” 3rd edition, published by Mac Millan; P.
"Chemie Photographique" by Grafikides,
It can be prepared by various commonly used methods such as the ammonia method, neutral method, and acid method, which are described in books such as those published by Paul Montel. The silver halide grains thus prepared were treated with a chemical sensitizer (e.g., sodium thiosulfate, N,N,N'-trimethylthiourea, monovalent gold thiocyanate complex salt, monovalent gold thiosulfate complex salt, first chloride). The sensitivity can be increased without coarsening the particles by heat treatment in the presence of tin, hexamethylenetetramine, etc.). Photographic emulsions may be spectral sensitized or supersensitized as necessary by using polymethine sensitizing dyes such as cyanine, merocyanine, and carbocyanine alone or in combination, or in combination with styryl dyes, etc. Can be done. Furthermore, various compounds can be added to the photographic emulsion of the photographic light-sensitive material used in the present invention in order to prevent a decrease in sensitivity and the occurrence of fog during the manufacturing process, storage, or processing of the light-sensitive material. These compounds are 4-hydroxy-6-methyl-1,3,3a,
A large number of compounds have been known for a long time, including 7-tetrazaindene-3-methyl-benzothiazole and 1-phenyl-5-mercaptotetrazole, as well as many heterocyclic compounds, mercury-containing compounds, mercapto compounds, and metal salts. . Examples of compounds that can be used include TH James and CEK Mees,
"The Theory of the Photographic Process"
The original document is listed in the 3rd edition (1966), published by MacMillan. When the silver halide photographic emulsion is used as a color photographic light-sensitive material, a coupler may be included in the silver halide emulsion layer. Such couplers are 4-equivalent type diketomethylene yellow couplers,
2-equivalent diketomethylene yellow coupler,
For example, US Patent No. 3277157, US Patent No. 3408194, US Patent No.
3551155, JP-A-47-26133, JP-A-48-66836, etc.; 4-equivalent or 2-equivalent pyrazolone magenta couplers and indazolone magenta couplers, such as U.S. Pat. No. 2,600,788;
Compounds described in U.S. Pat. No. 3214437, U.S. Pat.
Compounds described in et al. are used. In addition, U.S. Patent No. 3227554, U.S. Patent No. 3253924, U.S. Patent No.
Coupler capable of releasing a development inhibitor described in No. 3379529, No. 3617291, No. 3770436, etc. can also be used. The silver halide emulsion layer 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 (singly or in combination). Typical examples include mucochloric acid, formaldehyde, trimethylolmelamine, glyoxal, 2,3-dihydroxy-
1,4-dioxane, 2,3-dihydroxy-5
-Aldehyde compounds such as methyl-1,4-dioxane, succinaldehyde, and glutaraldehyde; divinyl sulfone, methylene bismaleimide, 1,3,5-triacryloyl-hexahydro-s-triazine, 1,3,5-trivinyl Sulfonyl-hexahydro-s-triazine bis(vinylsulfonylmethyl)ether, 1,3-
Active vinyl compounds such as bis(vinylsulfonyl)propanol-2, bis(α-vinylsulfonylacetamido)ethane; 2,4-dichloro-
Active halogen compounds such as 6-hydroxy-s-triazine sodium salt, 2,4-dichloro-6-methoxy-s-triazine; 2,4,6-
Examples include ethyleneimine compounds such as triethyleneimino-s-triazine. A surfactant 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 photographic property improvements, and charge sequence adjustment. These surfactants include natural surfactants such as saponin, nonionic surfactants such as alkylene oxide, glycerin, and glycidol, higher alkylamines, quaternary ammonium salts, pyridine and other heterocycles, 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;
These are amphoteric surfactants such as amino acids, aminosulfonic acids, and sulfuric acid or phosphoric acid esters of amino alcohols. It is also possible to use fluorine-based surfactants for the same purpose. Some examples of surfactant compounds that can be used include U.S. Pat. No. 2,271,623, U.S. Pat.
No. 2739891, No. 3068101, No. 3158484,
No. 3201253, No. 3210191, No. 3294540, No.
No. 3415649, No. 3441413, No. 3442654, No. 3441413, No. 3442654, No.
No. 3475174, No. 3545974, No. 3666478, No.
No. 3507660, British Patent No. 1198450, and Ryohei Oda et al., “Synthesis of surfactants and their applications (Maki Shoten,
1964) and Surf S Active Agents by A. W. Perry (Interscience Publications, Inc., 1958),
It is described in books such as JP Sisley's Encyclopedia of Active Agents Volume 2 (Chemical Publishing Company, 1964). In the present invention, when a fluorine-containing surfactant is used in combination, it is highly effective in preventing static marks. Examples of fluorine-containing surfactants that can be used in combination include the following compounds. For example, British Patent Nos. 1330356 and 1524631, U.S. Patent No. 3666478, U.S. Patent No. 3589906,
26687, JP-A No. 49-46733, JP-A No. 51-32322,
There are fluorine-based surfactants described in et al. To give a typical example of a compound, for example, N-
Perfluorooctylsulfonyl-N-propylglycine potassium salt, 2-(N-perfluorooctylsulfonyl-N-ethylamine)ethyl phosphate, N-[4-(perfluorononenyloxy)benzyl]-N,N-dimethyl Ammonioacetate, N-[3-(N',N',N'-trimethylammonio)propyl]perfluorooctylsulfonamide iodide, N-(polyoxyethylenyl)-N-propylperfluorooctylsulfonamide _{( C8F17SO2N ( C3H7 )}
(CH ₂ CH ₂ O) _o H) and fluorine-containing succinic acid compounds. In addition, in the present invention, lubricating compositions such as U.S. Pat. No. 3,079,837, U.S. Pat.
No. 3545970, No. 3294537 and Japanese Published Patent No. 1972
Modified silicones such as those shown in No.-129520 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. May include methyl methacrylate and the like. By implementing the present invention, failures caused by statics that occur during the manufacturing process and/or during use of photographic light-sensitive materials have been improved. Unexpected effects of practicing the present invention include contact between the emulsion side and the back side of photographic materials, contact between emulsion surfaces and materials with which photographic materials commonly come into contact, such as rubber, metals, and plastics. Also, the occurrence of static marks caused by contact with fluorescent screens etc. was significantly reduced. Next, the effects of the present invention will be specifically explained with reference to Examples, but the present invention is not limited thereto. Note that the adhesion test in the examples was conducted by the following method. (1) Adhesion test during drying Use a razor blade to make scratches at approximately 4 mm intervals on the emulsion side of the raw film and the dried film that has been processed, and then apply adhesive tape (manufactured by Sumitomo 3M Co., Ltd.) on top of the scratches. Apply Scotch Permacel Tape and peel it off instantly. If the peeled area is less than 0-5% by this method, it is grade A, 5-30%.
If it is less than 30%, it is grade B, and if it is 30 to 100%, it is grade C. (2) Wet adhesion test At each stage of development, fixing, and washing, scratch the emulsion surface of the film in the processing solution with a steel pen.
Apply it crosswise and rub the scratched area with your fingertips in a direction perpendicular to the line. If the emulsion layer does not peel beyond the scratches, it is graded A. If the maximum peeling width is within 5 mm, it is graded B. If it is larger than this, it is graded C. Example 1 65 parts by weight of stannic chloride hydrate and 1.5 parts by weight of antimony trichloride were dissolved in 1000 parts by weight of ethanol to obtain a homogeneous solution. A 1N aqueous sodium hydroxide solution was added dropwise to this solution until the pH of the solution reached 3 to obtain a coprecipitate of colloidal stannic oxide and antimony oxide. The resulting coprecipitate was left at 50°C for 24 hours to obtain a reddish brown colloidal precipitate. A reddish-brown colloidal precipitate was separated by centrifugation. In order to remove excess ions, water was added to the precipitate and the precipitate was washed with water by centrifugation. This operation was repeated three times to remove excess ions. 100 parts by weight of the colloidal precipitate from which excess ions have been removed are mixed with 50 parts by weight of barium sulfate with an average particle size of 0.3μ and water.
A powder mixture of stannic oxide and barium sulfate with an average particle size of 0.1 μm and a bluish color was obtained by mixing 1000 parts by weight and spraying into a firing furnace heated to 900°C. Put 1 g of this mixture into an insulating cylinder with an inner diameter of 1.6 cm, and use stainless steel electrodes from the top and bottom to measure 1000 kg/cm ^2.
The specific resistance of the powder was measured while being pressurized at a pressure of 11 Ω-cm. Example 2 A mixture consisting of 10 parts by weight of the SnO ₂ powder obtained in Example 1 and 40 parts by weight of water was adjusted to pH 6.5 using 1N NaOH solution, and then dispersed in a paint shaker for 1 hour to ensure uniform dispersion. I got the liquid. This dispersion
Centrifugation was performed at 1000 rpm for 30 minutes to remove coarse particles. The concentration of this liquid was 14% by weight. this
Mix SnO ₂ liquid, 10% by weight gelatin liquid with pH 6.5, and distilled water in the following mixing ratio, and then add 5 weight of polyamide/polyamine/epichlorohydrin reaction product (Kaimen-557) to the gelatin solid content. % and coated on a support that had been subjected to corona discharge treatment using a wire bar. After coating this undercoat layer, it was dried at 140°C for 5 minutes.

[Table] After leaving the obtained support under the conditions of 25°C and 10% RH for 2 hours, the surface resistance value of the second undercoat layer was measured using an insulation resistance measuring device (Model VE-30 manufactured by Kawaguchi Electric Co., Ltd.). It was measured. Further, the light scattering of this support was measured using a light scattering meter (manufactured by Narumi Co., Ltd.). In addition, a silver halide emulsion for X-rays (AgBrI, I = 2.5 mol%) was applied to this undercoated support at a rate of 3 silver per square meter.
g and 3.5 g of gelatin was coated and dried, and the adhesive strength was measured. The results are as follows and the volume% of _SnO2 is 50
% has good charging characteristics and the emulsion layer adheres to the support very strongly.

[Table] <Comparative sample without adding crosslinking agent> The same sample as in Example 2 was mixed with Kaimen-557.
When the adhesive force was measured using a sample made without the addition of , the degree of adhesion when wet was poor.

[Silver halide emulsion composition]

Binder: 9.15 g of gelatin/80 g of emulsion Silver halide composition: AgI 8.5 mol% and
AgBr91.5mol%BExcess20mol% Silver amount: 4.42×10 ^-2 mol% Average grain size of silver halide grains: 0.75 μm [Additive composition] Potassium polyvinylbenzenesulfonate (2% solution); 2c.c./emulsion 80g Sodium dodecylbenzenesulfonate (1% solution); 2 c.c./per 80 g of emulsion [Dispersion conditions of SnO ₂ powder/water dispersion] 5 mg, 20 mg of SnO ₂ powder in 34 c.c. of water, respectively.
80mg and 200mg dispersions. Four types of silver halide emulsions containing SnO ₂ powder with the above content were applied to a 100 μm polyethylene terephthalate film so that the dry coated silver amount was 3.2 to 3.3 g/m ² , and dried to form SnO ₂
A silver halide photographic material containing powder was prepared. For comparison, a silver halide photographic material containing no SnO ₂ powder was prepared using a similar formulation. Next, the material created in this way, and then this material was dried in a dry thermostat (50℃, 20% RH for 7 days).
The materials subjected to wet thermography (50° C., 80% RH for 7 days) were examined for fog and sensitivity of the silver halide emulsion layer. D76 developer (manufactured by Eastman Kodak) was used as the developer, and the development conditions were 20° C. and 8 minutes. As shown in Table 6, no increase in fog was observed due to the presence or absence of SnO ₂ particles.

[Table] Furthermore, when we compared the sensitivity at the concentration of Fog Plus 0.2, we found that it was almost independent of the presence or absence of SnO 2 particles and the amount of SnO ₂ particles.
When the sensitivity of the comparison material without SnO ₂ particles is set to 100, those subjected to dry thermometry showed a sensitivity of 112, and those subjected to wet thermometry showed a sensitivity of 63. (Incidentally, only the sample containing 200 mg of SnO ₂ and subjected to wet thermography showed a sensitivity of 100.) As a result, the use of the conductive metal oxide used in the present invention improves photographic properties as shown in the silver halide emulsion. It was found that there was no effect on Example 4 A mixture consisting of 100 parts by weight of zinc oxide, 5 parts by weight of a 10% aqueous solution of Al(NO ₃ ) ₃ ·9H ₂ O and 100 parts by weight of water was irradiated with ultrasonic waves for 10 minutes to obtain a uniform dispersion. After drying this dispersion at 110°C for 1 hour,
×10 ^-4 Torr, baked at 600℃ for 5 hours, specific resistance 2×
Zinc oxide of 10 ² Ω-cm was obtained. The particle size was 2μ.
These particles are crushed using a ball mill to obtain an average particle size of
Particles of 0.7μ were obtained. Example 5 A mixture consisting of 10 parts by weight of the ZnO powder obtained in Example 4 and 150 parts by weight of water was dispersed in a paint shaker for 1 hour to obtain a uniform dispersion. This dispersion
Coarse particles were removed by centrifugation at 1000 rpm for 30 minutes. The remaining supernatant was centrifuged at 2000 rpm for 1 hour to obtain a ZnO paste consisting of fine particles. 10 parts by weight of the above ZnO paste was mixed with 25 parts by weight of 10% gelatin aqueous solution, 100 parts by weight of water, and 2 parts of 1,3,5-triglycidyl isocyanurate, and dispersed in a paint shaker for 1 hour to prepare a subbing liquid. . This coating solution was applied to a corona-treated film in the same manner as in Example 2 to give a dry weight of 2 g/m ² to obtain a conductive support. This support was left under conditions of 25° C. and 25% RH for 2 hours, and the surface resistance was measured to be 3×10 ⁹ Ω.

Claims (1)

[Claims] 1 After performing electron impact treatment on at least one side of the photographic support material, ZnO, TiO ₂ ,
At least one crystalline metal oxide selected from SnO ₂ , Al ₂ O ₃ , In ₂ O ₃ , MgO, BaO, MoO ₃ or a composite oxide thereof, or a small amount of foreign atoms contained therein A photographic support comprising a subbing layer comprising fine particles having a volume resistivity of 10 ⁷ Ω-cm or less, a hydrophilic binder, and a curing agent for the hydrophilic binder. body.