JPH0685060B2 - Silver halide photographic light-sensitive material - Google Patents

Description

Detailed Description of the Invention

[Field of Industrial Application] The present invention relates to a silver halide photographic light-sensitive material. INDUSTRIAL APPLICABILITY The present invention can be used, for example, as a photosensitive material for obtaining a copied image of an original image by directly exposing an original image having image information such as characters and pictures to a silver halide photographic light-sensitive material and then performing development processing and the like. it can. BACKGROUND OF THE INVENTION Photographic light-sensitive materials, especially light-sensitive materials having a reflective support, are conventionally large in thickness, and are inconvenient when files with images are formed, affixed to albums, or used in various designs. is there. Therefore, a photographic light-sensitive material having a small thickness is desired. However, conventional photosensitive materials
As the support, a support having a thickness of about 200 to 250 μm is generally used, and a thin support as a reflective support has not been put to practical use. Even if you try to thin the photosensitive material, with a thin support, there are many jamming such as winding around the roller when developing with an automatic developing machine, winding around the roller especially during drying, and wrinkles caused by sticking. This is because practical application is difficult. [Object of the Invention] The present invention is a silver halide photographic light-sensitive material having a small thickness, and even when it is automatically processed, there is no trouble such as jamming such as winding around a roller or jamming. Therefore, it is an object of the present invention to provide an advantageous photographic light-sensitive material that can be effectively used as a light-sensitive material for various purposes, for example, for forming a copy image. [Structure and Action of the Invention] As a result of earnest studies by the present inventors, the present inventors have found that a silver halide photographic light-sensitive material having a silver halide emulsion layer on a reflective support has a Taber stiffness of 0.8 to 4.0. The above object can be achieved by using a hydrophilic colloid layer having a dry film thickness of 3 to 15 .mu.m containing fine particle powder on the surface of the reflective support opposite to the side having the silver halide emulsion layer. I found a thing. To obtain a light-sensitive material having a small thickness, the support may be made thin, but the present inventors have found that a thin support has low rigidity as a result of various studies, and this is the cause of troubles, and therefore, Even if the support has a Taber stiffness of about 0.8 to 4, various means for preventing the above problems have been studied, and fine particles are provided on the surface of the reflective support opposite to the side having the silver halide emulsion layer. It has been found that the above object can be achieved by providing a hydrophilic colloid layer containing a powder and having a dry film thickness of 3 to 15 μm. In the present invention, the Taber stiffness of the support (Ta-ber STIF
FNESS) is a Taber V-5 stiffness measuring instrument as a measuring instrument.
Model 150B T-aberV-5 Stiffness teste-r (TABER I
NSTRUMENT-A TELEDYNE COMPANY). The Taber stiffness may be in the range of 0.8 to 4.0. Note that the support generally has different stiffness values in the vertical direction and the lateral direction, but at least one of the supports may be within this range. Various materials can be arbitrarily used as the material of the reflective support. For example, a reflective support having a water resistant surface such as polyolefin laminated paper or synthetic paper is preferably used. The waterproof surface can be formed by coating a hydrophobic resin on a substrate, for example, a paper substrate, and such a hydrophobic resin coating layer can be formed on both surfaces of the photosensitive material. In the embodiment in which such a water-resistant surface is formed, it is possible to prevent the substrate from being watered even when the silver halide photographic light-sensitive material is immersed in a bath used for the development processing. Examples of the resin used for the hydrophobic resin coating layer coated on the back surface include polyolefins such as polyethylene, polypropylene and polybutene, olefins such as ethylene, propylene and butene, and monomers such as vinyl acetate, vinylidene chloride and maleic anhydride. (For example, ethylene-vinyl acetate copolymer, propylene-vinylidene chloride copolymer, propylene-maleic anhydride copolymer, etc.), or polystyrene, polyvinyl chloride, polyacrylate, saturated polyester, polycarbonate Homopolymers or copolymers such as nates,
Alternatively, blended substances of these may be used. The thickness of this hydrophobic resin coating layer is not particularly limited, but generally 15 to 50
About μm is preferable. The hydrophobic resin layer coated on the side of the substrate (paper or the like) on which the silver halide emulsion layer is provided is preferably formed mainly of polyethylene resin. This polyethylene resin includes a homopolymer of ethylene and a copolymer of ethylene and other components. Other components copolymerizable with ethylene include, for example, α such as propylene and butene-1.
-Olefins, vinyl compounds such as styrene, vinyl stearate, vinyl acetate, acrylic acid, methacrylic acid, acrylamide, etc., esters of vinyl carboxylic acid compounds such as methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, acrylic acid And a metal salt of methacrylic acid, a diene compound such as butadiene and isoprene. The polyethylene resin is not particularly limited in its molecular weight as long as it can be extrusion coated, but the molecular weight is usually 20,0
Polyethylene in the range of 00 to 200,000 is used. The polyethylene resin used for the hydrophobic resin coating layer in this case may be any of low density, medium density and high density polyethylene resins, and these may be used alone or in combination of two or more kinds. In order to form such a hydrophobic resin coating liquid by coating such a hydrophobic resin on a paper substrate, various coatings can be used. A particularly common coating method is the extrusion coating method. When a hydrophobic resin coating is provided to form a water-resistant surface, a light-reflecting substance such as titanium oxide, zinc oxide, calcium carbonate or calcium sulfate can be added to make an image clear. These substances may be used alone or in admixture of two or more, for example, about 5 to 25 parts by weight relative to 100 parts by weight of the resin.
It can be added in the range of parts by weight. Such an opaque layer can be provided on the surface of the support, for example.
When a hydrophobic resin layer containing such a light-reflecting substance is used, it is not necessary to coat it with a variator layer or the like to impart reflectivity even when a paper substrate is used. The silver halide photographic light-sensitive material of the present invention has a hydrophilic colloid layer having a dry film thickness of 3 to 15 μm containing fine particle powder on the surface of the reflective support opposite to the side having the silver halide emulsion layer. The fine particle powder of the present invention is often referred to in the art as a matting agent, and therefore is hereinafter referred to as a matting agent unless otherwise specified. As the matting agent that can be used in the present invention,
For example, crystalline or amorphous silica, titanium dioxide,
Magnesium oxide, calcium carbonate, barium sulfate, strontium barium sulfate, magnesium aluminate silicate, silver halide, silicon dioxide, acrylic acid-ethyl acrylate copolymer, acrylic acid-methyl methacrylate copolymer, itaconic acid-styrene copolymer , Maleic acid-methyl methacrylate copolymer, maleic acid-styrene copolymer, acrylic acid-phenyl acrylate copolymer, polymethyl methacrylate, acrylic acid-methacrylic acid-ethyl methacrylate copolymer, polystyrene, starch, cellulose acetate pro Peonate and the like, other U.S. Pat.No. 1,221,980,
Examples thereof include the compounds described in No. 2,992,101 and the like, and these can be used alone or in combination of two or more kinds. Colloidal silica may be used together with the matting agent. The matting agent preferably has an average particle size of 1 to 10 μm, more preferably 3 to 10 μm. The average particle diameter as used herein is the average value of the diameter of spherical particles, and the diameter of a cube or particles of a shape other than spherical when the projected image is converted into a circular image of the same area. Then, when its particle size is ri and its number is ni, it is defined by the following equation. As a specific measuring method, the method described in JP-A-59-29243 can be used. In the present invention, the matting agent is dispersedly contained in the layer on the side opposite to the color-sensitive layer.
If necessary, in a hydrophilic binder containing a nonionic, cationic or anionic surfactant, other additives are added as necessary, a high-speed rotating mixer, a homogenizer,
It can be formed by dispersing by an ultrasonic dispersion, a ball mill, or the like by an emulsion dispersion method utilizing shear stress, and coating by an arbitrary method. The coating amount of the matting agent in the layer to contain a matting agent, 1 m ² per 50~500mg are preferably Ku to be contained, more preferably it is contained 70~300mg per 1 m ^2. Further, the content of the matting agent is preferably 3 to 50 Wt%, more preferably 5 to 20 Wt% with respect to the hydrophilic binder. Any layer can be used as the silver halide emulsion layer formed on the support of the photographic light-sensitive material of the present invention.
A black-and-white light-sensitive emulsion can be used to form a black-and-white light-sensitive material, or a color light-sensitive emulsion can be formed in a single layer or a multilayer to form a single-color or multi-color color light-sensitive material. Positive type photographic light-sensitive materials (direct positive image-forming photographic light-sensitive materials using internal latent image-type silver halide emulsions, fog-breaking direct positive image-forming photographic light-sensitive materials, reversal color light-sensitive materials, silver bleach-type light-sensitive materials, etc.) Can also be embodied as When embodied as a color photographic light-sensitive material for direct positive image formation, for example, on one side of the support, a red-sensitive direct positive silver halide emulsion layer containing a cyan coupler, a green-sensitive direct positive silver halide emulsion layer containing a magenta coupler. A constitution having a silver halide emulsion layer, a yellow filter layer and a blue-sensitive direct positive silver halide emulsion layer containing a yellow coupler can be adopted. These layers may be formed by sequentially applying the layers in the order described above from the support side. As the coupler contained in each of the color-sensitive layers, the yellow dye-forming coupler is a benzoylacetanilide type, a pivaloylacetanilide type, or a so-called split-off group capable of leaving a carbon atom at the coupling position during coupling. Substituted 2-equivalent yellow couplers and the like are useful. As the magenta dye-forming coupler, a 5-pyrazolone type, a pyrazolotriazole type, a pyrazolinobenzimidazole type, an indazolone type, or a 2-equivalent type magenta coupler having a split-off group is useful. Further, as a cyan dye forming coupler, a phenol type,
A 2-equivalent cyan coupler having a naphthol type, a pyrazoquinazolone type, or a split-off group is useful. These dye-forming couplers can be arbitrarily selected, and the usage method, usage amount, etc. are not particularly limited. Further, an ultraviolet absorber can be used to prevent fading of the dye image due to short-wavelength actinic rays, and examples thereof include thiazolidone, benzotriazole, acrylonitrile, and benzophenone compounds.
120, 320, 326, 327, and 328 (all manufactured by Ciba-Geigy) are preferably used alone or in combination. In the practice of the present invention, in addition to the silver halide emulsion layers such as the above red, green and blue color sensitive layers and the hydrophilic binder layers on the opposite side thereof, a protective layer, an intermediate gelatin layer, or a lower layer, if necessary. An antihalation layer or the like may be formed on. When the light-sensitive material of the present invention is embodied as a direct positive image-forming silver halide photographic light-sensitive material, an emulsion which can be used is, for example, an internal latent image type silver halide emulsion. For example, a so-called conversion type silver halide emulsion by the conversion method described in U.S. Pat.
No. 3,206,316, No. 3,317,322 and No. 3,367,778, and silver halide emulsions having internally chemically sensitized silver halide grains, or U.S. Pat.
No. 3,447,927 and No. 3,531,291, a silver halide emulsion having a silver halide grain containing a polyvalent metal ion, or a silver halide grain containing a dopant described in U.S. Pat. , A silver halide emulsion in which the grain surface is weakly chemically sensitized;
-8524, No. 50-38525 and No. 53-2408, so-called core-shell type silver halide emulsions by the laminating method, and others, JP-A-52-156614, 55-127549 and 57.
The silver halide emulsion described in JP-A-79940 can be used. In this case, the internal latent image type silver halide is particularly preferably made of laminated grains. Such a silver halide can be produced in the same manner as a usual laminated silver halide. For example, JP-A-50-852
No. 4, No. 50-38525, No. 53-60222, No. 55-1524 and U.S. Pat.No. 3,206,313, etc., silver chloride grains are formed and then converted to silver bromide grains by adding bromide. Further, a method of laminating a halide by adding silver nitrate, or making silver iodobromide grains in a state where there is little excess halogen, and further adding silver chloride,
Examples thereof include a method of sequentially laminating silver bromide. Regarding the composition of the silver halide grains inside the laminated type or core / shell type, silver iodobromochloride grains having a high silver bromide content (60 to 100 mol%) are suitable. The composition of the silver halide laminated on the outside is preferably silver chlorobromide, and it is desirable that the silver chloride ratio is high (70 mol% or more) from the viewpoint of developability. As the grain size of the silver halide, a grain size of 0.2 to 1.7 μm can be used. When high contrast is required, a narrow grain size distribution is preferable, and when low contrast is required, the grain size is small. Good with a wide size distribution. Various photographic additives can be added to the internal latent image type silver halide emulsion. For example, as optical sensitizers that can be used, cyanines, merocyanines, trinuclear or tetranuclear merocyanines, trinuclear or tetranuclear cyanines, styryls, holopolar cyanines, hemicyanines, oxonols and hemioxo are known. Examples thereof include knols. The internal latent image type silver halide emulsion can be supersensitized. Regarding the method of supersensitization, for example, “Review of Supersensitization Mechanism” Review of Super-sensitization Photographic Science and Engineering (Phot
ographic Science and Engineering) (PSE) Vol.18,
See page 4418 (1974). When an internal latent image type silver halide emulsion is used, the emulsion usually contains a stabilizer, such as a compound having an azaindene ring, for keeping the surface sensitivity as low as possible and imparting a lower minimum density and more stable properties. And a heterocyclic compound having a mercapto group can be contained. As the compound having an azaindene ring, for example, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene is preferable. Further, among the heterocyclic compounds having a mercapto group, the nitrogen-containing heterocyclic compound is a pyrazole ring, 1,2,4
-Triazole ring, 1,2,3-triazole ring, 1,3,4-thiadiazole ring, 1,2,3-thiadiazole ring, 1,2,4-thiadiazole ring, 1,2,5-thiadiazole ring, 1 , 2,3,4-
A tetrazole ring, a pyritazine ring, a 1,2,3-triazine ring, a 1,2,4-triazine ring, a 1,3,5-triazine ring, etc., and a ring in which two or three of these rings are condensed, for example, triazolo ring. Examples thereof include a triazole ring, a diazaindene ring, a triazaindene ring, a tetrazaindene ring, a pentazaindene ring, a phthalazinone ring, an indazole ring, and the like, and 1-phenyl-5-mercaptotetrazole is particularly preferable. In addition, a wetting agent is used according to the purpose, and examples of the wetting agent include dihydroxyalkane and the like,
Further, as the film physical property improver, for example, by emulsion polymerization of a copolymer of alkyl acrylate or alkyl methacrylate with acrylic acid or methacrylic acid, styrene-maleic acid copolymer, styrene maleic anhydride half alkyl ester copolymer and the like. The resulting water-dispersible particulate polymer substance is suitable, and examples of the coating aid include saponin, polyethylene glycol, lauryl ether and the like. Other photographic additives include gelatin plasticizers, surfactants, UV absorbers, pH
It is optional to use a regulator, an antioxidant, an antistatic agent, a thickener, a graininess improver, a dye, a modulant, a whitening agent, a development speed regulator, a matting agent, an anti-irradiation dye or the like. The silver halide photographic light-sensitive material of the present invention may contain appropriate gelatin (including oxidized gelatin) and its derivatives depending on the purpose. Examples of this preferable gelatin derivative include acylated gelatin, guanidylated gelatin, carbamylated gelatin, cyanoethanolated gelatin, esterified gelatin and the like. Further, in the silver halide photographic light-sensitive material of the present invention,
In addition to gelatin, the hydrophilic colloid layer may contain other hydrophilic binder. This hydrophilic binder can be used as a binder for an emulsion layer or a hydrophilic colloid layer formed on the side opposite to the emulsion, or for the purpose of forming a photographic constituent layer such as an intermediate layer, a protective layer, a filter layer and a backing layer. Can be added according to
Furthermore, the hydrophilic binder may contain an appropriate plasticizer, lubricant or the like depending on the purpose. The photographic constituent layers of the light-sensitive material of the present invention can be hardened with any suitable hardener. Examples of these preferable hardeners include chromium salts, zirconium salts, aldehyde compounds such as formaldehyde and mucohalogen acid, halotriazine compounds, polyepoxy compounds, ethyleneimine compounds, vinylsulfone compounds, acryloyl hardeners and the like. To be Further, the silver halide photographic light-sensitive material of the present invention comprises an emulsion layer on the support and a matting agent-containing layer on the side opposite to the emulsion layer,
As described above, various photographic constituent layers such as a filter layer, an intermediate layer, a protective layer, an undercoat layer, a backcoat layer, an antihalation layer and the like are coated and produced as needed. As the coating method, dip coating, air doctor coating, extrusion coating, slide hopper coating, curtain flow coating and the like can be used. In the present invention, in the case of directly forming a positive image using the internal latent image type silver halide photographic light-sensitive material, the main step is to subject the internal latent image type silver halide photographic light-sensitive material which has not been fogged in advance to imagewise exposure. It is common to carry out surface development after the fog treatment or while performing the fog treatment. The fog treatment can be performed by uniformly exposing the entire surface or using a fog agent. in this case,
The uniform exposure on the entire surface is preferably performed by immersing or moistening the image-exposed internal latent image type silver halide photographic light-sensitive material in a phenomenon liquid or another aqueous solution, and then uniformly exposing the entire surface. The light source used here may be any light within the photosensitive wavelength range of the internal latent image type silver halide photographic light-sensitive material, and can be irradiated with high illuminance light such as flash light for a short time, or weak light. Light may be irradiated for a long time. The time of uniform exposure over the entire surface can be varied within a wide range so that the best positive image can be finally obtained depending on the internal latent image type silver halide photographic light-sensitive material, the development processing conditions, the type of light source used, and the like. A wide variety of compounds can be used as the fog agent, and the fog agent only needs to be present at the time of development processing, for example, in an internal latent image type silver halide photographic light-sensitive material such as a silver halide emulsion layer or It may be contained in the developing solution or the processing solution prior to the developing treatment, but it is preferably contained in the internal latent image type silver halide photographic light-sensitive material (among them,
Especially good in a silver halide emulsion layer). The amount used can be varied over a wide range according to the purpose, and a preferable amount to be added is, when added to the silver halide emulsion layer,
1 to 1500 mg per mol of silver halide, particularly preferably
It is 10 to 1000 mg. Further, when added to a processing solution such as a developing solution, a preferable addition amount is 0.01 to 5 g / l, particularly preferably 0.
It is from 08 to 0.15 g / l. Examples of such fogging agents include hydrazines described in U.S. Pat.Nos. 2,563,785 and 2,588,982, or hydrazides described in U.S. Pat.No. 3,227,552, or hydrazone compounds: U.S. Pat. Issue 3,7
Heterocycle No. 4 described in Nos. 34,738 and 3,759,901
Secondary nitrogen compounds: Further, acylhydrazinophenyl thioureas described in U.S. Pat. No. 4,030,925 can be mentioned. Also,
These fogging agents can also be used in combination. For example, Research Disclos
(ure) No. 15162 describes that a non-adsorption type fogging agent is used in combination with an adsorption type fogging agent, which is also applicable to the present invention. Specific examples of useful fogging agents include hydrazine hydrochloride,
Phenylhydrazine hydrochloride, 4-methylphenylhydrazine hydrochloride, 1-formyl-2- (4-methylphenyl) hydrazine, 1-acetyl-2-phenylhydrazine, 1-acetyl-2- (4-acetamidophenyl) )
Hydrazine, 1-methylsulfonyl-2-phenylhydrazine, 1-benzoyl-2-phenylhydrazine,
Examples thereof include hydrazine compounds such as 1-methylsulfonyl-2- (3-phenylsulfonamidophenyl) hydrazine and formaldehydephenylhydrazine. When the present invention is applied to an internal latent image type silver halide photographic light-sensitive material, a positive image is directly formed by subjecting the material to imagewise exposure followed by exposure to light or development in the presence of a fogging agent. As a developing treatment method for the light-sensitive material, any developing treatment method is adopted, and a surface developing treatment method is preferable. This surface development processing method means processing with a developing solution which does not substantially contain a silver halide solvent. In carrying out the present invention, a positive image (visual image) corresponding to the original image can be formed by subjecting the exposed silver halide photographic light-sensitive material to a treatment with a processing solution having a developing treatment and a fixing ability. The above-mentioned development processing includes a combination of black-and-white development and color development as in color reversal processing, in addition to color development processing. Further, the entire surface exposure as in the processing of an internal latent image type silver halide photographic light-sensitive material or the development processing in the presence of a fogging agent is also included. The primary aromatic amino-based color developing agent used in the color developing processing in the present invention includes various kinds widely used in various color photographic processes. These developers contain aminophenol-based and p-phenylenediamine-based derivatives. These compounds are generally used in the form of salts, such as the hydrochloride or sulphate, for their stability in the free state. Also, these compounds are generally used at a concentration of about 0.1 g to about 30 g for color developer 1, and more preferably at a concentration of about 1 g to about 15 g for color developer 1. Examples of aminophenol-based developers include o-aminophenol, p-aminophenol and 5-amino-2-
Oxy-toluene, 2-amino-3-oxy-toluene, 2-oxy-3-amino-1,4-dimethyl-benzene and the like are included. Particularly useful primary aromatic amino color developing agents are N, N-dialkyl-p-phenylenediamine compounds, where the alkyl and phenyl groups may or may not be substituted. Among them, examples of particularly useful compounds include N, N-diethyl-p-phenylenediamine hydrochloride, N-methyl-p-phenylenediamine hydrochloride, N.
N-dimethyl-p-phenylenediamine hydrochloride, 2-amino-5- (N-ethyl-N-dodecylamino) -toluene, N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4- Aminoaniline sulfate, N-ethyl-N-β-hydroxyethylaminoaniline, 4-amino-methyl-N, -diethylaniline, 4-amino-N
Examples include-(2-methoxyethyl) -N-ethyl-3-methylaniline-p-toluenesulfonate. The alkaline color developing solution which can be used in the present invention is, in addition to the first aromatic amino color developing agent, various components which are usually added to the color developing solution, such as sodium hydroxide, sodium carbonate and potassium carbonate. Alkali agents such as, alkali metal bisulfites, alkali metal thiocyanates, alkali metal halides, benzyl alcohol, water softeners and thickeners may optionally be contained. The pH value of this color developing solution is usually 7 or higher, most commonly about 10 to about 13. The fixing processing solution in the case of carrying out the present invention is a processing solution containing a soluble complexing agent which is solubilized as a silver halide complex salt, and not only a general fixing solution but also a bleach-fixing solution, a one-bath development fixing solution, A one-bath development bleach-fix solution is also included, but a bleach-fix solution is preferred. Examples of the soluble complexing agent include thiosulfates such as potassium thiosulfate, sodium thiosulfate and ammonium thiosulfate, thiocyanates such as potassium thiocyanate, sodium thiocyanate and ammonium thiocyanate, thiourea, thioether and high concentration Typical examples are bromide and iodide, but the inclusion of thiosulfate is particularly effective for stabilizing the dye image over time, chemical stability and the ability to form a soluble complex with silver halide. Is desirable. After the color development processing, it is processed with a processing solution having a fixing ability. In the color processing, when the processing solution having a fixing ability is a fixing solution, a bleaching process is performed before that. As the bleaching agent used in the bleaching solution or the bleach-fixing solution used in the bleaching step, a metal complex salt of an organic acid is used, and the metal complex salt oxidizes the metal silver produced by development to convert it into silver halide. It has a function of coloring the uncolored part of the color forming agent, and its structure is an organic acid such as aminopolycarboxylic acid or oxalic acid, citric acid, and iron, cobalt,
The metal ions such as copper are coordinated. The most preferable organic acid used for forming such a metal complex salt of an organic acid includes polycarboxylic acid or aminopolycarboxylic acid. These polycarboxylic acids or aminopolycarboxylic acids may be alkali metal salts, ammonium salts or water-soluble amine salts. The following can be mentioned as specific representative examples of these. [1] Ethylenediaminetetraacetic acid [2] Diethylenetriaminepentaacetic acid [3] Ethylenediamine-N- (β-oxyethyl)-
N, N ', N'-triacetic acid [4] Propylenediaminetetraacetic acid [5] Nitrilotriacetic acid [6] Cyclohexanediaminetetraacetic acid [7] Iminodiacetic acid [8] Dihydroxyethylglycine Citric acid (or tartaric acid)

[9] Ethyletherdiaminetetraacetic acid [10] Glycoletherdiaminetetraacetic acid [11] Ethylenediaminetetrapropionic acid [12] Phenylenediaminetetraacetic acid [13] Ethylenediaminetetraacetic acid disodium salt [14] Ethylenediaminetetraacetic acid tetra (trimethylammonium) ) Salt [15] Ethylenediaminetetraacetic acid tetrasodium salt [16] Diethylenetriaminepentaacetic acid pentasodium salt [17] Ethylenediamine-N- (β-oxyethyl)-
N, N ', N'-triacetic acid sodium salt [18] Propylenediaminetetraacetic acid sodium salt [19] Nitrilotriacetic acid sodium salt [20] Cyclohexanediamine tetraacetic acid sodium salt The bleaching solution used is an organic acid as described above. In addition to containing the metal complex salt of 1) as a bleaching agent, various additives can be included. As the additive, it is particularly preferable to contain an alkali halide or an ammonium halide, for example, a rehalogenating agent such as potassium bromide, sodium bromide, sodium chloride, ammonium bromide, a metal salt, a chelating agent and the like. Alternatively, pH buffers such as borate, oxalate, acetate, carbonate, and phosphate, and those known to be added to ordinary bleaching solutions such as alkylamines and polyethylene oxides can be appropriately added. . Further, the fixing solution and the bleach-fixing solution, ammonium sulfite, potassium sulfite, ammonium bisulfite, potassium bisulfite, sodium bisulfite, ammonium metabisulfite, potassium metabisulfite, sulfite salts such as sodium metabisulfite, boric acid, Contain one or more pH buffers consisting of various salts such as borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, ammonium hydroxide. You can When processing is carried out while replenishing the bleach-fixing solution (bath) with a bleach-fixing replenishing solution, the bleach-fixing solution (bath) may contain thiosulfate, thiocyanate, sulfite or the like. The replenisher may contain these salts to replenish the treatment solution (bath). Further, in order to increase the activity of the bleach-fixing solution, air or oxygen may be blown in the bleach-fixing bath and the storage tank for the bleach-fixing replenisher, if desired, or a suitable oxidizing agent such as peroxide may be used. Hydrogen, bromate, persulfate and the like may be added appropriately. After the treatment with the treatment liquid having the fixing ability, a usual washing treatment may be carried out, but particularly when carrying out the present invention, it is preferable to carry out a stabilizing treatment which substantially does not include a post-washing step. Stabilization treatment that does not substantially include a water washing step means immediately after the treatment with a processing solution having a fixing ability, the stabilization treatment by a single-tank or multi-tank countercurrent method. Treatment steps other than general washing with water such as washing with water and a known washing accelerating bath may be included. In the stabilization processing step, the method of bringing the stabilizing solution into contact with the silver halide light-sensitive material is preferably to immerse the silver halide photographic light-sensitive material in a bath like a general processing solution, but sponge, synthetic fiber cloth It may be applied to the emulsion surface of the silver halide photographic light-sensitive material, both sides of the conveyor leader, the conveyor belt, or sprayed with a spray or the like. Hereinafter, the case where the stabilizing bath by the dipping method is used will be mainly described. The stabilizing solution preferably contains a chelating agent having a chelate stability constant for iron ions of 6 or more. Examples of the chelating agent having a chelate stability constant of 6 or more for iron ions include organic carboxylic acid chelating agents, organic phosphoric acid chelating agents, inorganic phosphoric acid chelating agents, and polyhydroxy compounds. The iron ion means ferric ion (Fe ³⁺ ). Specific examples of the chelating agent having a chelate stability constant of 6 or more with ferric ion include diethylenetriaminepentaacetic acid, nitrilotriacetic acid, and 1-hydroxyethylidene-1,1-diphosphonic acid. The amount of the chelating agent used is 0.01 to 50 per stabilizing solution.
g, preferably in the range of 0.05 to 20 g. Further preferred compounds to be added to the stabilizing solution are:
Examples thereof include antifungal agents, water-soluble metal salts, ammonium compounds and the like. Examples of the antifungal agent include isothiazoline type, benzisothiazoline type, and thiapendazole type. Further, as the metal salt, Ba, Ca, Ce, Co, In, La, Mn, Ni, Pb, S
n, Zn, Ti, Zr, Mg, Al, is a metal salt of Sr, halide,
It can be supplied as an inorganic salt such as a hydroxide, a sulfate, a carbonate, a phosphate, an acetate or a water-soluble chelating agent. The amount used is in the range of 1 × 10 ^-4 to 1 × 10 ^-1 mol, preferably 4 × 10 ^-4 to 2 × 10 ^-2 mol, and more preferably 8 × 10 ^-4 to ¹ mol of the stabilizing solution. It is in the range of 1 × 10 ^-2 mol. The amount of the above compound added to the stabilizing solution is 0.01 to 50 g, preferably 0.05 to 20 g per stabilizing solution. In addition to the above compounds, the stabilizing solution contains a fluorescent whitening agent, an organic sulfur compound, an onium salt, a hardener, a quaternary salt, a polyethylene oxide derivative, a siloxane derivative, and other water drop unevenness preventing agents.
PH buffering agents such as boric acid, citric acid, phosphoric acid, acetic acid, or sodium hydroxide, sodium acetate, potassium citrate, etc.
Improving treatment effects with organic solvents such as methanol, ethanol and dimethylsulfoxide, dispersants such as ethylene glycol and polyethylene glycol, and other color tone adjusting agents,
Adding various additives for expansion is optional. As a method of adding the above-mentioned compound and other additives, it is added as a concentrated liquid to the stabilizing tank, or the above-mentioned compound and other additives are added to the stabilizing solution supplied to the stabilizing tank, and this is stabilized. There are various methods such as whether to supply it to the solution or to add it to the pretreatment bath of the stabilization processing step to make it contained in the silver halide photographic light-sensitive material to be present in the stabilization tank. It may be added by such an addition method. When the stabilizing solution is supplied in the stabilization treatment step in a multi-tank countercurrent system, it is preferable to supply the stabilizing solution to the post-bath and allow the overflow from the pre-bath. The pH value of the treatment liquid in the stabilizing bath is preferably pH 4 to 8. The pH can be adjusted by the above-mentioned pH adjuster. The treatment temperature at the time of stabilization treatment is, for example, 20 ° C to 50 ° C,
It is preferably in the range of 25 ° C to 40 ° C. Also, the processing time is preferably as short as possible from the viewpoint of rapid processing, but it is usually 20 seconds to 5 seconds.
Minutes, most preferably 30 seconds to 2 minutes. In the multi-tank countercurrent method, it is preferable that the treatment is performed in a shorter time in the first-stage tank and longer in the second-stage tank. In the practice of the present invention, the washing treatment may not be carried out before and after the stabilizing treatment, but the surface is washed with a rinse or sponge by washing with a small amount of water within a short time and the stabilization of the image and the silver halide photographic light-sensitive material It is optional to provide a treatment tank for adjusting the surface physical properties of. Activators such as formalin and its derivatives, siloxane derivatives, polyethylene oxide compounds, and quaternary salts are used to stabilize the image and adjust the surface properties of the silver halide photographic material. In practicing the present invention, it is optional to provide additional processing steps in addition to the above processing steps. In addition to the above-mentioned stabilizing solution, silver may be recovered by a known method from a processing solution containing a soluble silver complex salt such as a fixing solution or a bleach-fixing solution. Further, if the stabilizing treatment as described above is performed, the water washing step is substantially unnecessary, and thus the piping equipment for the water washing treatment is unnecessary,
There is an advantage that the device itself can be easily installed in any place. [Examples] Examples of the present invention will be described in detail below, but the present invention is not limited to these embodiments. A sample was prepared as follows. A gelatin layer having the following composition was applied to the back surface (transparent polyethylene layer) side of a surface-treated polyethylene laminated paper having a Taber stiffness of 2.2 and dried. The surface (white polyethylene layer containing 15 wt% titanium oxide)
Nine emulsion layers according to the following were provided on the side to prepare a direct positive type color light-sensitive material. (Emulsion layer etc.) Preparation of Emulsion S A 750 ml of 2.0% inactive gelatin solution was kept at 50 ° C., and the following solutions A1 and B were added at the same time with stirring, and the mixture was injected over 3 minutes. After aging for 25 minutes, excess salt was removed by a precipitation water washing method and then re-dispersed, and C1 liquid and D1 liquid were added. After 10 minutes, excess water-soluble salt was removed again, and a small amount of gelatin was added to disperse the silver halide grains. Preparation of Emulsion L While keeping 750 ml of 1.5% inactive gelatin solution at 60 ° C., Solution A2 and Solution B were added at the same time with stirring, and the mixture was injected over 15 minutes. After aging for 40 minutes, excess salt was removed by a precipitation water washing method, redispersion was performed, 10 mg of hypo was added, and then C2 solution and D2 solution were added. After 10 minutes, excess water-soluble salt was removed again, and a small amount of gelatin was added to disperse the silver halide grains. Preparation of Emulsion M While maintaining 750 ml of 2.0% inactive gelatin solution at 50 ° C., the following solution A3 and solution B were added at the same time with stirring, and the mixture was injected over 5 minutes. After aging for 25 minutes, excess salt was removed by a precipitation water washing method, and then the mixture was redispersed and C1 liquid and D2 liquid were added. After 10 minutes, excess water-soluble salt was removed again, and a small amount of gelatin was added to disperse the silver halide grains. A sensitizing dye, a coupler and the like were added to these three types of emulsions to prepare a multilayer color light-sensitive material. Red photosensitive emulsion layer (first layer) Sensitizing dye [D-3] for emulsion S and emulsion M,
[D-4], stabilizer [T-1], [T-2], surfactant [S-2], further dibutyl phthalate, ethyl acetate,
A protected dispersed coupler solution containing the surfactant [S-2], 2,5-dioctylhydroquinone and the uncoupler [CC-1], [CC-2] was added. Add 5% gelatin (Emulsion S: Emulsion M) (weight ratio)
Mixed so that the amount of coated silver is 0.4 g / m ² , and the amount of coated gelatin is
Apply so that it will be 1.8 g / m ² . First intermediate layer (second layer) Dioctyl phthalate, 2,5-dioctyl hydroquinone, UV absorber Tinuvin 328 (manufactured by Ciba Geigy),
A gelatin solution containing a liquid in which a protective dispersion containing a surfactant [S-1] is dispersed is prepared and applied so that the applied amount of tinuvin is 0.15 g / m ² and the applied amount of gelatin is 1.08 g / m ² . Green sensitive emulsion layer (third layer) Sensitizing dye [D-2], stabilizer [T] for emulsion S and emulsion M
-1], [T-2], and a surfactant [S-2], and further dibutyl phthalate, ethyl acetate, 2,5-dioctylhydroquinone, a surfactant [S-1], a magenta coupler [MC-1. ] Was added to the protected dispersion coupler solution. Add gelatin and hardener [H-1] to prepare emulsion
S: Emulsion M is mixed at a ratio of 5: 5 (weight ratio), and the silver coating amount
0.43 g / m ^2, is coated to a gelatin coating amount 1.5 g / m ^2. Second intermediate layer (fourth layer) The same formulation as the first intermediate layer is applied so that the coating amount of Tinuvin 328 is 0.2 g / m ² and the coating amount of gelatin is 0.7 g / m ² . Yellow filter layer (fifth layer) Yellow colloidal silver and dioctyl phthalate, ethyl acetate, surfactant [S- which is formed by oxidizing under a weak alkaline reducing agent (weak reducing agent is removed by a noodle washing method after neutralization) 1], a protected dispersion containing 2,5-dioctylhydroquinone, a surfactant [S-2] and a hardener [H-1] are added to colloidal silver coating amount of 0.15 g / m ² , gelatin coating amount. Apply to 1.0g / m ² . Third intermediate layer (sixth layer) Same as the first intermediate layer. Blue-sensitive emulsion amount (seventh layer) Sensitizing dye [D-1] for emulsion L and emulsion M, respectively
Stabilizer [T-1], [T-3], surfactant [S-
2], and further, a protect-dispersed coupler solution containing dibutyl phthalate, ethyl acetate, 2,5-dioctylhydroquinone, a surfactant [S-1] and a yellow coupler [Y-1] was added. Add gelatin and hardener [H-1] to prepare emulsion
L: Emulsion M is mixed at a ratio of 5: 5 (weight ratio), and the silver coating amount
The coating amount is 0.55 g / m ² and the gelatin coating amount is 1.7 g / m ² . Third intermediate layer (eighth layer) dioctyl phthalate, 2,5-dioctyl hydroquinone, ultraviolet absorber Tinuvin 328, surfactant [S-1]
Providing a protected dispersed gelatin solution containing, Tinuvin coating amount 0.5 g / m ^2, coated so that gelatin coating amount 0.9 g / m ^2. Protective layer (9th layer) Colloidal silica, coating aid [S-2], hardener [H-
2], a gelatin solution containing [H-3] is used to apply a gelatin coating amount of 0.8 g / m ² . As described above, Samples 1 to 6 prepared by forming an emulsion layer and a gelatin layer on the front surface and the back surface, respectively, and changing the amount of the fine particle powder in the gelatin layer as shown in Table 1 were processed in the following steps. Processing process (processing temperature and processing time) [1] Immersion (color developing solution) 38 ° C 8 seconds [2] Fog exposure-10 seconds at 1 lux [3] Color development 38 ° C 2 minutes [4] Bleach fixing 35 ° C 60 Sec [5] Stabilizing treatment 25-30 ° C 1 min 30 sec [6] Drying 75-80 ° C 1 min Treatment composition (color developer) Benzyl alcohol 10 ml Ethylene glycol 15 ml Potassium sulfite 2.0 g Potassium bromide 1.5 g Sodium chloride 0.2g Potassium carbonate 30.0g Hydroxylamine sulfate 3.0g Polyphosphoric acid (TPPS) 2.5g 3-Methyl-4-amino-N-ethyl-N- (β-methanesulfonamidoethyl) -aniline sulfate 5.5g Fluorescent enhancement Whitening agent (4,4'-diaminostilbenzsulfonic acid derivative) 1.0 g Potassium hydroxide 2.0 g Water is added to bring the total amount to 1 and the pH is adjusted to 10.20. (Bleach-fixing solution) ethylenediaminetetraacetic acid ferric ammonium dihydrate
60g Ethylenediaminetetraacetic acid 3g Ammonium thiosulfate (70% solution) 100ml Ammonium sulfite (40% solution) 27.5ml Potassium carbonate or glacial acetic acid Adjust the pH to 7.1 and add water to bring the total volume to 1. (Stabilizing liquid) 5-chloro-2-methyl-4-isothiazolin-3-one 1.0 g Ethylene glycol 10 g 1-Hydroxyethylidene-1,1'-diphosphonic acid 2.5 g Bismuth chloride 0.2 g Magnesium chloride 0.1 g Ammonium hydroxide (28% aqueous solution) 2.0g Sodium nitrilotriacetate 1.0g Add water to make the total amount 1 and adjust the pH to 7.0 with ammonium hydroxide or sulfuric acid. Each sample was imagewise exposed as described above, developed using the automatic processor shown in FIG. 1, and dried. The effect of the present invention was confirmed by the occurrence rate of jamming of the sample in the dry part. The results are also shown in Table 1. In the automatic processor, the sample passes through the developing tank 1 containing the developing solution, the bleach-fixing tank 2 containing the bleach-fixing solution, and the stabilizing tanks 3a and 3b containing the stabilizing solution, and is dried in the drying section 4. . 5 is a saucer. The liquid is a countercurrent system. The warm air for drying is dried by blowing air heated by an electric heater to the drying section from above and below by a fan. From Table 1, it can be seen that the jamming is significantly reduced by providing the hydrophilic binder layer containing the fine particle powder on the back surface (Comparison between Sample 1 and Samples 2 to 5). Sample 6
There was less jamming, but it was poorly dried. Further, when a similar test was conducted using Sample 7 provided only on the emulsion layer side using a thick reflective support having a Taber stiffness of 19.5, the jamming occurrence rate was 0.9%, and the Taber stiffness used in the present invention was determined. It was found that the occurrence of jamming can be suppressed to the level of the thick support of Sample 7 even with a low reflection support. Furthermore, instead of the reflective support having a Taber stiffness of 2.2, a sample was also prepared for a reflective support having a Taber stiffness of 1.3, and a similar test was conducted.As a result, those with a dry film thickness of 8.0, 5.6, 12.6, 4.3μ also showed poor drying. No jamming rate is 1.5, 2.2, 1.
It was confirmed to be 0,6.0%, which is significantly improved compared to 45% of the sample containing no fine particle powder. [Effects of the Invention] As described above, the silver halide photographic light-sensitive material of the present invention has a small thickness, and even when it is automatically processed, it may cause problems such as jamming such as winding around a roller or jamming. Therefore, it can be effectively used as a photosensitive material for various purposes, for example, for forming a copy image.

[Brief description of drawings]

FIG. 1 is a schematic cross-sectional view showing an example of an automatic processor used for testing a sample. 1 ... Development bath, 2 ... Bleach-fix bath, 3a, 3b ... Stabilization bath,
4 ... Drying section.

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Claims (1)

[Claims] 1. A silver halide photographic light-sensitive material having a silver halide emulsion layer on a reflective support, wherein the reflective support has a Taber stiffness of 0.8 to 4.0, and the reflective support has the silver halide emulsion. A silver halide photographic light-sensitive material comprising a hydrophilic colloid layer containing a fine particle powder and having a dry film thickness of 3 to 15 μm on the surface opposite to the layer-containing side.