JPH0120734B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a silver halide photographic material with improved antistatic properties (hereinafter referred to as "photographic material").
In particular, it relates to a photographic light-sensitive material with improved antistatic properties without adversely affecting photographic properties. Photographic materials generally consist of an electrically insulating support and a photographic layer, so they may be exposed to contact friction or peeling from surfaces of the same or different materials during the manufacturing process and during use. static charges often build up. This accumulated static charge causes many problems, but the most serious problem is that the accumulated static charge is discharged before processing, and the light-sensitive photographic emulsion layer is exposed to light, and when the photographic film is processed, It causes dot-like spots or dendritic or feather-like streaks. 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 problem becomes apparent only after the image is developed, 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. 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, 3938998, etc., e.g.
No. 2982651, No. 3428456, No. 3457076, No. 3457076, 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 dielectric properties of many of these materials are dependent on humidity, and they have a major drawback in that they lose their function as 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 is It is a material that is humidity dependent 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 hardly depends on humidity, and secondary oxide are used as conductive materials for conductive supports of electrophotographic photoreceptors or electrostatic recording materials. It is known to use metal oxides such as tin and indium oxide. However, the use of these conductive materials in tin halide photographic materials is completely unknown. Furthermore, images obtained using light-sensitive photographic materials are
It may be observed by transmitted light or printed on photographic paper, and in this case, the light transmittance of the areas without images must be sufficiently high. Therefore, the materials that can be used for the conductive paper for electrophotography or electrostatic recording cannot necessarily be used as they are for silver halide photographic light-sensitive materials. 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 light-sensitive materials without impairing photographic properties. A fourth object of the present invention is to provide a photographic material suitable for observing images using transmitted light. The object of the present invention is to provide a conductive layer in which conductive fine particles that dissolve in the photographic processing steps of development, fixation, and water washing are dispersed in a binder with the back layer or silver halide photographic emulsion layer of a light-sensitive silver halide photographic material. It turns out that this can be achieved by installing it between the body and the body. That is, the present invention has an average particle size of 0.5 to 5.0 μm.
and has at least one conductive layer in which zinc oxide particles having a volume resistivity of 107 Ω-cm or less or zinc oxide particles having a different type of atom, which are substantially dissolved in the photographic development process, are dispersed in a binder. This is a silver halide photographic light-sensitive material. Since the conductive layer used in the present invention is dissolved during the processing process, even if the conductive layer has haze or coloring, it disappears and the film becomes a highly transparent film suitable for image observation. It becomes a film. Furthermore, since the conductive layer of the present invention is provided between the back layer or photographic emulsion layer and the support, even if haze or coloration occurs due to conductive particles before processing, there will be no adverse effect on photographic properties. The conductive zinc oxide used in the present invention is generally obtained by doping zinc oxide with other atoms, such as aluminum or indium. The volume resistivity of the conductive particles of the present invention is preferably 10 ⁷ Ω-cm or less, preferably 10 ⁵ Ω-cm or less. In the present invention, there is no problem even if there is haze before photographic processing, so the particle size does not necessarily have to be sufficiently small, but it is preferably 5μ or less.
3μ or less is better. 0.5μ in patent application 1984-47663
Although the following particles are used, larger particles may be used in the present invention without any problem. In order to provide the conductive layer of the present invention, process-soluble conductive particles may be dispersed in a binder and applied. Examples of the binder include gelatin, modified gelatin, polyvinyl alcohol, vinyl alcohol copolymer, carboxymethylcellulose, polyacrylic acid, acrylic acid copolymer, polyvinylpyrrolidone, vinylpyrrolidone copolymer, hydroxyethyl acrylate copolymer, etc. Water-soluble polymers, cellulose derivatives such as acetylcellulose, acetylbutylcellulose, acetylpropylcellulose, phthaloxyacetylcellulose, styrene, α-methylstyrene, hydroxystyrene, vinyl acetate, alkyl (carbon number 1 to 4)
(alkyl group) acrylate, alkyl (alkyl group having 1 to 4 carbon atoms) methacrylate, homopolymers such as vinyl chloride, vinylidene chloride, copolymer containing these monomers, copolymer containing maleic anhydride, soluble nylon, soluble polyester etc. can be mentioned. In order to show specific examples of the photosensitive silver halide photographic material containing the conductive layer of the present invention, cross-sectional views thereof are shown in FIGS. 1 to 5. Figures 1 and 2 show cases in which a conductive layer is provided between the support 1 and the photographic emulsion layer 2, and the conductive layer 3 and the undercoat layer 4 may be provided separately as shown in Figure 1. ,
Further, as shown in FIG. 2, the conductive layer and the undercoat layer may be used together. Figures 3 to 5 show the case where the conductive layer is provided on the opposite side to the photographic emulsion layer.
The figure shows an undercoat layer 8 when a conductive layer 7 is provided on the back.
FIG. 5 shows a method in which a layer 9 having functions such as matteness, slipperiness, and scratch resistance is provided on the conductive layer shown in FIG. 4. 1 to 5 show typical examples, and it is needless to say that the present invention is not limited thereto. A crosslinking agent, dispersant, surfactant, matting agent, etc. that react with the binder may be added to the conductive layer of the present invention. Examples of dispersants include sodium metaphosphate,
Examples include phosphates such as sodium pyrophosphate. In order to provide the layer of the present invention, a dispersion of conductive particles dispersed in a binder may be applied, and water or a common organic solvent can be used as the solvent for the dispersion. Examples of organic solvents include alcohols such as methanol, ethanol, and propanol, esters such as methyl acetate and ethyl acetate, chlorinated hydrocarbons such as methylene dichloride, ethylene dichloride, ethane tetrachloride, and chlorocene, acetone, and methyl ethyl ketone. , ketones such as methyl isobutyl ketone, and other examples include methyl cellosolve, ethyl cellosolve, dioxane, methyl cellosolve acetate, benzene, phenol, resorcinol, and cresol. These solvents can be used alone or in combination. As a coating method for preparing these dispersions, air knife coating, gravure coating, roller bead coating, bar coating, extrusion coating, etc. can be used. The supports used in the present invention may be those commonly used as photographic supports, such as cellulose triacetate, cellulose acetate butyrate, polycarbonate, polystyrene, polyethylene naphthalate, polyethylene naphthalate, polyolefin laminated paper, etc. It can be raised. The structures of the light-sensitive silver halide emulsion layer and other layers of the photographic light-sensitive material of the present invention are not particularly characterized, and any known materials can be used. For example, hydrophilic colloids such as gelatin, silver halides, sensitizers, antifoggants, hardeners, surfactants, polymer latexes, color couplers,
Regarding anti-fading agents, ultraviolet absorbers, fluorescent whitening agents, matting agents, slip agents, spectral sensitizing dyes, etc., please refer to Research Disclosure Magazine (Hesearch
Disclosure) Vol. 176, pages 22-29 (December 1978). In the present invention, any known method can be used for photographically processing the photographic material. A known treatment liquid can be used. The processing temperature is usually chosen between 18°C and 50°C, but temperatures below 18°C or above 50°C may also be used.
Depending on the purpose, either a development process for forming a recorded image (black photographic process) or a color photographic process consisting of a development process for forming a dye image can be applied. The developer used in black-and-white photographic processing can contain known developing agents. As developing agents, dihydroxybenzenes (for example, hydroquinone), 3-pyrazolones (for example, 1
-phenyl-3-pyrazolidone), aminophenols (e.g. N-methyl-p-aminophenol), 1-phenyl-3-pyrazolines, ascorbic acid, and the 1,2,3, Heterocyclic compounds in which a 4-tetrahydroquinoline ring and an indolene ring are condensed can be used alone or in combination.
The developing solution generally contains other well-known preservatives, alkaline agents, PH buffers, antifoggants, etc., and, if necessary, solubilizing agents, color toners, development accelerators, surfactants, antifoaming agents, etc. It may also contain water softeners, hardeners, viscosity-imparting agents, and the like. As the fixer, one having a commonly used composition can be used. As the fixing agent, in addition to thiosulfates and thiocyanates, organic sulfur compounds known to be effective as fixing agents can be used. The fixing agent may contain a water-soluble aluminum salt as a hardening agent. When forming a dye image, conventional methods can be applied. Negative-positive method (e.g. “Journal of the Society
of Motion Picture and Television
Engineers, Volume 61 (1953), pp. 667-701), developed in a developer containing a black and white developing agent to produce a negative silver image, followed by at least one uniform exposure or other suitable fogging. process,
The color reversal method, in which a dye-positive image is obtained by subsequent color development, and the silver dye bleaching method, in which a photographic emulsion layer containing dyes is exposed and developed to create a silver image, and this is used as a bleaching catalyst to bleach the dyes. It will be done. Color developers generally consist of an alkaline aqueous solution containing a color developing agent. The color developing agent is a known primary aromatic amine developer, such as phenylenediamines (e.g., 4-amino-N,N-diethylaniline, 3-methyl-4-amino-N,N-diethylaniline, 4-amino- N-ethyl-N-β
-Hydroxyethylaniline, 3-methyl-4-
Amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfamide ethylaniline,
4-amino-3-methyl-N-ethyl-N-β-
methoxyethylaniline, etc.) can be used. Other Photography by LFAMason
Processing Chemistry (Focal Press, 1966)
pages 226-229, U.S. Patent No. 2193015, U.S. Patent No. 2592364
JP-A No. 48-64933, etc. may be used. After color development, the photographic emulsion layer is usually bleached. The bleaching process may be performed simultaneously with the fixing process, or may be performed separately. Bleach agents include iron (), cobalt (), chromium (), and copper ().
Compounds of polyvalent metals such as, peracids, quinones, nitroso compounds, etc. are used. For example, ferricyanide, dichromate, organic complex salts of iron () or cobalt (), aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, 1,3-diamino-2-propanoltetraacetic acid, or citric acid, tartaric acid. , complex salts of organic acids such as malic acid; persulfates, permanganates;
Nitrosophenols and the like can be used.
Of these, potassium ferricyanide, sodium ferric ethylenediaminetetraacetate, and ammonium ferric ethylenediaminetetraacetate are particularly useful. Ethylenediaminetetraacetic acid iron() complex salts are useful in both stand-alone bleach solutions and single bath bleach-fix solutions. The present invention will be explained in more detail with reference to Examples below, but the present invention is not limited to these Examples. Example 1 A mixture consisting of 100 parts by weight of zinc oxide, a 10% aqueous solution of 5 parts by weight of Al( _NO3 ) _3.9H2O , 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, 600℃ for 5 minutes, volume resistivity 2
A conductive zinc oxide of ×10 ² Ω-cm was obtained. Particle size is 2μ
It was hot. These particles were ground in a ball mill to obtain particles with an average particle size of 0.7μ. Take 25g of the above conductive zinc oxide and add 400c.c. of distilled water.
Added to a solution of 0.3g of sodium metaphosphate,
The mixture was dispersed for 1 hour using Paint Sheaker (manufactured by Toyo Seiki Seisakusho). Add gelatin 2.4% (by weight) aqueous solution 300 to this dispersion.
cc was added and dispersed for 5 minutes using a paint shaker. This dispersion was added as a gelatin hardening agent (CH ₂ =
CH−SO ₂ −CH ₂ −CONH (− ₂ CH ₂ was added to make a coating solution. A 100μ thick polyethylene terephthalate film was undercoated with vinylidene chloride/ethyl acrylate/acrylic acid (85:10:5) copolymer latex. A sample was prepared by coating the conductive zinc oxide dispersion at 15 c.c./m ² on the prepared support and drying it at 135°C for 10 minutes.This sample was designated as (A).As a comparative sample, chloride A 1.2% aqueous solution of gelatin as a hardening agent (CH ₂ = CH−SO ₂ −CH ₂ −CONH) − ₂ CH ₂ on vinylidene copolymer latex basecoat.
Apply 30 c.c. of solution per 1 ^m2 and heat at 135℃ for 10
After drying for a minute, a sample was prepared and designated as (B). The surface resistivity of samples (A) and (B) was measured at 25°C, 25%RH and
Measurement was carried out under two conditions: 25°C and 60%RH. The measured values are shown in the table below, and sample (A) was in the 10 ⁹ Ω range under all conditions, but samples (B) to which conductive zinc oxide was not added were all 10 ¹⁴ or higher.

[Table] The upper silver halide photographic emulsion layer for indirect X-rays of samples A and B was coated to prepare a photosensitive material for indirect X-rays. As a result of measuring the haze after developing this photosensitive material, both (A) and (B) were 7%, and no difference was observed. Example 2 Conductive zinc oxide of Example 1 55 parts by weight Nitrocellulose 5 Methyl ethyl ketone 320 parts by weight The liquid mixture having the above composition was dispersed in a paint shaker for 30 minutes. 60 g of acetone and 60 g of methanol were added to the above dispersion and stirred to obtain a coating liquid. This coating solution was applied to a 127 μ thick cellulose triacetate base at a rate of 20 c.c./m ² and dried at 120° C. for 10 minutes. Furthermore, the following solution was applied on top of this layer at a rate of 10 c.c./m ² . Cellulose diacetate 1 part by weight Acetone 100 Methanol 60 Behenic acid amide 0.01 The surface of the support opposite to this layer was undercoated with gelatin, and a micro silver halide emulsion was coated to prepare a micro photosensitive material. The surface resistivity of the surface of this film coated with conductive zinc oxide is 3× ¹⁰ Ω at 25°C and 10%RH.
It showed excellent antistatic properties. Further, the haze of this film after processing was 5%, which was good. Example 3 A support consisting of a 180μ polyethylene terephthalate film was treated with a corona discharge and then subbed with gelatin. The gelatin dispersion of conductive zinc oxide used in Example 1 was coated on one side so that the dry film thickness was 1 μm. A silver halide emulsion for medical X-rays was coated on both sides of this support to prepare a photosensitive material for X-rays (Sample A). As a comparison sample, sample (B) was prepared by coating a silver halide emulsion directly on a gelatin undercoat. The emulsion side of the film was rubbed with white rubber in a dark room at 25°C and 25% RH, and developed. Sample A
No static marks were observed in sample B, but static marks were observed in sample B. Further, the haze after development was 8% in all cases.

[Brief explanation of drawings]

1 to 5 are cross-sectional views of typical photographic materials according to the present invention. In each figure, 1 is a support, 2 is a photosensitive silver halide emulsion layer, 3 is a conductive layer, 4 is an undercoat layer, 5 is a back layer, 6 is a back conductive layer, 7 is a conductive layer, and 8 is a back layer. The subbing layer for the back conductive layer, 9 represents the back overcoat layer.

Claims (1)

[Claims] 1. A conductive material in which zinc oxide particles having an average particle size of 0.5 to 5.0 μm and a volume resistivity of 107 Ω-cm or less, which are substantially dissolved in the photographic development process, or zinc oxide particles having a foreign atom are dispersed in a binder. A silver halide photographic material comprising at least one layer.