JPH0120733B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a silver halide photographic material with improved antistatic properties, and particularly to a photographic material with improved antistatic properties without adversely affecting photographic properties. Photographic light-sensitive materials generally consist of a support and a photographic layer that have electrical insulation properties. Electrostatic charges often build up. This accumulated electrostatic charge causes many problems, but
The most serious problem is that the photosensitive emulsion layer becomes sensitized due to the discharge of electrostatic charges accumulated before processing, resulting in dot-like spots or dendritic or feather-like line spots when the photographic film is processed. It is something that happens. This is what is called a static mark, and it significantly reduces the commercial value of the photographic film, or in some cases completely destroys it. 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. Furthermore, these accumulated electrostatic charges may cause secondary failures such as dust adhering to the film surface or inability to apply uniformly. As mentioned above, such electrostatic charges are often accumulated during the production and use of photographic materials. This occurs due to separation of the support surface and emulsion surface, etc. In addition, in the finished product, separation of the base surface and emulsion surface when winding and switching photographic film is performed, or mechanical parts or fluorescent sensitization in an automatic X-ray film camera. This occurs due to contact separation between the paper and the paper. It can also occur due to contact with other packaging materials.
Static marks on photographic materials induced by such electrostatic charge accumulation become more noticeable as the sensitivity of photographic materials increases and the processing speed increases. Particularly in recent years, static marks are more likely to occur due to the increased sensitivity of photographic materials and the increased exposure to harsh handling such as high-speed coating, high-speed photography, and high-speed automatic processing. There is. 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 accumulated charge is discharged. Therefore, methods have been considered to improve the conductivity of supports and various coated surface layers of photographic materials, including the use of various hygroscopic substances, water-soluble inorganic salts, certain surfactants, and polymers. It has been tried. For example, US Patent No. 2882157, US Patent No. 2972535,
No. 3062785, No. 3262807, No. 3514291, No. 3514291, No.
3615531, 3753716, 3938999, etc., e.g.
No. 2982651, No. 3428456, No. 3457076, No.
Surfactants such as those described in US Pat. No. 3,454,625, US Pat. No. 3,552,972 and US Pat. No. 3,655,387 and colloidal silica as described in US Pat. No. 3,525,621 are known. However, many of these materials exhibit specificity depending on the type of film support and photographic composition, giving good results with some film supports, photographic emulsions, and other photographic components, but not with others. Vine film supports and photographic components are not only completely useless in preventing static electricity, but may also have an adverse effect on photographic properties. More importantly, the electrical conductivity of many of these materials is dependent on humidity, and they have a major drawback in that they lose their function as electrically conductive layers under low humidity conditions. 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, for example, U.S. Patent No. 3062700,
-113224 and No. 55-12927, etc., crystalline zinc oxide whose conductivity is almost independent of humidity, It is known to use metal oxides such as tin and indium oxide. However, it is completely unknown that these crystalline metal oxide particles can be used as antistatic agents in silver halide emulsions, and furthermore, it is unclear how these conductive materials interact with the silver halide photosensitive emulsion layer. It was completely unpredictable whether he would have it or not. Incidentally, silver halide and copper halide are used as the conductive materials described in U.S. Patent No. 3,245,833, but these conductive materials are not compatible with the silver halide emulsion layer as shown in U.S. Pat. No. 3,428,451. It has been clearly shown that there is an interaction between the two, which has an adverse effect on photographic properties. A first object of the present invention is to provide an antistatic photographic material. A second object of the present invention is to provide a photographic material with excellent antistatic properties even at low humidity. A third object of the present invention is to provide an effective method for preventing charging of photographic materials without impairing their photographic properties. These objects of the invention _include ZnO, _TiO2 , _SnO2 , _{Al2O3 , In2O3} , _SiO2 ,
Fine particles of at least one crystalline metal oxide selected from MgO, BaO, _MoO3 , or a composite oxide thereof, and the fine particles are produced by (1) calcination, and then mixed with different atoms. (2) Fine particles obtained by coexisting different atoms when produced by calcination.(3) Fine particles obtained by lowering the oxygen concentration and eliminating oxygen defects when produced by calcination. A photographic material having improved antistatic properties, characterized in that a silver halide photographic light-sensitive material is provided with at least one conductive layer containing any of the introduced fine particles dispersed in a binder. This is accomplished using photosensitive materials. Crystalline metal oxide particles are preferable as conductive particles used in the present invention, but particles containing oxygen defects and particles containing a small amount of foreign atoms that form donors for the metal oxide used are generally used. Generally speaking, it is particularly preferred because it has high conductivity, and the latter is especially preferred because it does not cause fog to the silver halide emulsion. Examples of metal oxides are ZnO,
_TiO2 , _SnO2 , _Al2O3 , _In2O3 , _{SiO2 ,} MgO _,
BaO, MoO ₃ , etc., or composite oxides thereof are preferable, and ZnO, TiO ₂ and SnO ₂ are particularly preferable. As an example of including different atoms, for example, for ZnO,
Addition of Al, In, etc., addition of Sb, Nb, halogen elements, etc. to SnO ₂ , and addition of Nb, Nb, etc. to TiO ₂ .
Addition of Ta etc. is effective. The amount of these different atoms added is preferably in the range of 0.01 mol% to 30 mol%, particularly preferably 0.1 mol% to 10 mol%. The usable particle size is preferably 10μ or less, but if it is 2μ or less, stability after dispersion is good and it is easy to use. In addition, in order to minimize light scattering, it is very preferable to use conductive particles with a size of 0.5 μm or less, as this makes it possible to form a transparent photosensitive material. The conductive fine particles made of a crystalline metal oxide used in the present invention are produced by the methods (1) to (3) described above. 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 cost. For example, in a method for obtaining SnO ₂ fine particles by spraying β-stannic acid colloid (amorphous), which is a hydrate of SnO ₂ , into a firing furnace,
- Conductive SnO ₂ fine particles can be obtained by coexisting hydrates of antimony chloride, antimony nitrate, antimony oxide, etc. in stannic acid colloid.
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. There is also a method of thermally decomposing an organic acid salt of a metal to obtain a metal oxide, in which salts of different metals are allowed to coexist during the thermal decomposition. An example of the third method is a vacuum evaporation method in which metals are evaporated in an oxygen atmosphere to obtain metal oxide fine particles, but the amount of oxygen is slightly insufficient, or metals and metal salts are not supplied with sufficient oxygen. There is a way to heat it. In the conductive layer according to the present invention, conventionally known conductive polymers can be used as part or all of the binder. These compounds include, for example, polyvinylbenzenesulfonic acid salts, polyvinylbenzyltrimethylammonium chloride, U.S. Pat.
Quaternary salt polymers described in US Pat. No. 4,070,189, OLS 2,830,767 (US Ser.
These include crosslinked polymer latexes described in No. 816127) and others. The amount of conductive particles used is preferably 0.05 to 20 g, particularly preferably 0.1 to 10 g, per square meter of the photographic material. In order to use the conductive particles more effectively and lower the resistance of the conductive layer, it is preferable that the volume content of the conductive particles in the conductive layer is high, but in order to have sufficient strength as a layer, it is preferable that the volume content of the conductive particles is at a minimum. It is preferable to include about 5% of the binder, and the volume content of the conductive particles is preferably in the range of 5 to 95%. 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 cellulose nitrate film, cellulose acetate film, cellulose acetate butyrate film, cellulose acetate propionate film, polystyrene film, polyethylene terephthalate film,
There are polycarbonate films and other laminates of these materials. More specifically, baryta or α-olefin polymers, particularly polyethylene, polypropylene, ethylene-butene copolymers, etc. with 2 carbon atoms
Examples include paper coated or laminated with a polymer of ~10 α-olefins. 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. When the adhesive strength between the support and the photographic emulsion layer is insufficient, a layer having adhesive properties to both is provided as an undercoat layer. In addition, to further improve adhesion, the surface of the support was treated with corona discharge.
Conventional preliminary treatments such as ultraviolet irradiation and flame treatment may be performed. 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 pinylpyrrolidone, 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-processed gelatin, acid-processed gelatin, and enzyme-processed 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
Mees, 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, dichloride dichloride). 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 3rd edition (1966), published by MacMillan, cites the original literature. 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-
Bis(vinylsulfonylmethyl)propanol-
2. Bis(α-vinylsulfonylacetamide)
Active vinyl compounds such as ethane; 2,4-dichloro-6-hydroxy-s-triazine sodium salt, 2,4-dichloro-6-methoxy-s-
Active halogen compounds such as triazines; 2,4,
Examples include ethyleneimine compounds such as 6-triethyleneimino-s-triazine. Surfactants may be added alone or in combination to the photographic 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 Sulfonium cationic surfactants; carboxylic acids,
These include anionic surfactants containing acidic groups such as sulfonic acid, phosphoric acid, sulfuric acid esters, and phosphoric acid esters, and amphoteric surfactants such as amino acids, aminosulfonic acids, and sulfuric or phosphoric acid esters of amino alcohols. It is also possible to use fluorine-containing 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 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. For example, in the practice of the present invention, contact between the emulsion side and the back side of a photographic light-sensitive material, contact between the emulsion side and the emulsion side, and materials with which photographic light-sensitive materials commonly come into contact, such as rubber, metals, plastics, and fluorescent light. The occurrence of static marks caused by contact with intensifying 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. Example 1 A mixture consisting of 100 parts by weight of stannic oxide (average particle size 1.0 μm), 10 parts by weight of a 10% methanol solution of antimony trichloride, and 50 parts by weight of methanol was ultrasonically dispersed for 10 minutes to obtain a uniform dispersion. This dispersion was dried at 110° C. for 1 hour and then calcined in air at 800° C. for 1 hour to obtain stannic oxide with a slightly bluish tint. The specific resistance was 6 Ω-cm when measured by molding it into a tablet at a pressure of 1000 Kg/cm ² . The particle size was approximately the same as the average particle size of the stannic oxide used. Particles of the same size with specific resistances of 25 Ω-cm and 200 Ω-cm were obtained from stannic oxide with average particle diameters of 0.5 μ and 0.2 μ, respectively. Example 2 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℃ for 1 hour,
10 ^-4 Torr Baked for 5 minutes at 600℃, specific resistance 2×10 ² Ω
−cm of zinc oxide was obtained. The particle size was 2μ. These particles were ground with a ball mill to produce an average particle size of 0.7μ.
particles were obtained. Example 3 100 parts by weight of tin metal and 1 part by weight of antimony metal were reacted with 400 parts by weight of concentrated nitric acid to obtain a colloidal precipitate consisting of antimonic acid and β-stannic acid. This precipitate was centrifuged and washed three times with 1,000 parts by weight of water, and then washed with 500 parts by weight of water.
The mixture was diluted to parts by weight to obtain a colloidal dispersion. This dispersion was sprayed into a calcining furnace heated to 800°C to obtain fine blue-tinged stannic oxide powder. This fine powder had a specific resistance of 3.2 Ω-cm and a particle size of 0.5 μm. Example 4 A mixture consisting of 100 parts by weight of titanium oxide, 10 parts by weight of a 10% methanol solution of niobium pentachloride, and 100 parts by weight of methanol was irradiated with ultrasonic waves for 10 minutes to obtain a uniform dispersion. After drying this dispersion at 110°C for 1 hour,
By firing at 750° C. and ×10 ⁻⁴ Torr for 5 minutes, a fine titanium oxide powder with a bluish tint was obtained. This fine powder has a specific resistance
The particle size was 6.2×10 ² Ω-cm and 1 μm. Example 5 10 parts of tin oxalate was placed in an electric furnace at 200°C/hr.
The sample was heated to 300°C at a heating rate of 300°C, held at 300°C for 2 hours, and then cooled and taken out. 7.2 parts of blackish brown fine particles (1μ or less) were obtained. The specific resistance of this material was ρν=1.8×10°Ωcm. Similarly, for those heated to 1000℃, the specific resistance ρν = 3
×10 ⁶ Ωcm. Example 6 Put 10 parts of tin oxalate into a thin container and add methylene chloride to the extent that the tin oxalate is submerged.
Tributoxyantimony (Sb(OC ₃ H ₇ ) ₃
Add 0.1 part of , stir, and warm to 80°C to distill off methylene chloride. It was heated to 800°C at a heating rate of 300°C/hr in an electric furnace, and then taken out from the electric furnace after being allowed to cool.
7.17 parts of fine particles (1μ or less) with a slight bluish tinge were obtained. The specific resistance of this material was ρν=1.3×10°Ωcm. Example 7 The conductive particles obtained in Examples 1 to 6 were dispersed in polyvinyl alcohol (PVA) and gelatin and applied to a polyethylene terephthalate (PET) film to prepare a conductive layer. The surface of PET film was treated with corona to improve its wettability. The results are summarized in Table 1. The particle to binder ratio was 5:1 by weight.

[Silver halide emulsion composition]

Binder: 9.15 g of gelatin/per 80 g of emulsion Silver halide composition: AgI 8.5 mol% and
AgBr91.5mol% Br ^- Excess20mol% Silver amount: 4.42×10 ^-2 mol% Average particle size of silver halide grains: 0.75 μm [Additive composition] Potassium polyvinylbenzenesulfonate (2% solution); 2c.c./ Sodium dodecylbenzenesulfonate (1% solution) per 80 g of emulsion; 2 c.c./per 80 g of emulsion [Dispersion conditions of SnO ₂ powder/water dispersion] 5 mg and 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 in a similar manner. Next, the materials created in this way, and the materials that were subjected to dry thermography (50℃, 20%RH or less for 7 days) and wet thermography (50℃, 80%RH for 7 days), were halogenated. The fog and sensitivity of the silver emulsion layer were investigated. D76 developer (manufactured by Eastman Kodak) was used as the developer, and the development conditions were 20° C. and 8 minutes. As a result, no increase in fog due to interaction between SnO ₂ powder and silver halide particles was observed. Also, no change in sensitivity of the silver halide emulsion was observed.

Claims (1)

[Claims] 1 ZnO, TiO ₂ , SnO ₂ , Al ₂ O ₃ , In ₂ O ₃ , SiO ₂ ,
Fine particles of at least one crystalline metal oxide selected from MgO, BaO, and MoO ₃ or composite oxides thereof, and the fine particles are produced by (1) calcination, and are then prepared by the presence of foreign atoms. (2) Fine particles that have been heat-treated at the bottom. (2) Fine particles that are obtained by coexisting with different atoms when they are produced by firing. (3) Those that are produced by lowering the oxygen concentration and introducing oxygen defects when they are produced by firing. A photographic light-sensitive material with improved antistatic properties, characterized in that the silver halide photographic light-sensitive material is provided with at least one conductive layer in which the fine particles are dispersed in a binder. .