JPS62108243A - Silver halide photographic sensitive material for forming direct positive picture image - Google Patents

Abstract

PURPOSE:To reduce thickness of a base and to retard deterioration of sharpness of a picture image, by using a base having a specified thickness and transmission density and constituting all of three silver halide emulsion layers of direct positive siliver halide emulsion having different color sensitivity to each other. CONSTITUTION:A photographic sensitive material is constituted of a red sensitive direct positive silver halide emulsion layer contg. Cyan coupler, a green sensitive direct positive silver halide emulsion layer contg. Magenta coupler, and, if necessary a yellow filter layer, and a blue sensitive direct positive silver halide layer contg. Yellow coupler, on a base having 80-150mum thickness. Since the base has >=0.7 transmission density, a direct positive silver halide photosensitive material having high sharpness is obtd. even if the thickness of the base is so small as 80-150mum.

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to a silver halide photographic material for direct positive image formation. The present invention can be used, for example, as a photosensitive material for obtaining a copy image of the original image by directly exposing an original image having image information such as text or pictures to a silver halide photographic material, and then performing a development process or the like. can. [Background of the Invention] Thin photographic materials are desired. However, supports for photographic light-sensitive materials, such as reflective photographic supports, have conventionally been used with a thickness of about 200 to 250 .mu.m. In recent years, conference materials and reports with images formed on photographic materials have been used, but the current materials using the above-mentioned support are too thick and bulk up when filed, making handling inconvenient. It looks like this. For this reason, efforts have been made to make prints thinner in silver halide photographic materials that are printed from negative films, and some of these materials have begun to be put into practical use, although the quality is unsatisfactory. However, in the positive image-forming silver halide photographic light-sensitive material to which the present invention is directed, it has been difficult to put it to practical use using a thin support. This is because if the support is made thinner, the opacity decreases and the sharpness decreases, making it difficult to obtain a photosensitive material with sufficient practicality. [Object of the invention] An object of the present invention is to provide a silver halide photographic light-sensitive material that is small in thickness, suppresses deterioration in sharpness, and has excellent practicality for direct positive image formation. With the goal. [Structure and operation of the invention] As a result of intensive research, the present inventors have developed a silver halide photograph having three silver halide emulsion layers with different color sensitivities containing a cyan coupler, a magenta coupler, and a yellow coupler on a support. The support has a thickness of 80 to 150 μm, a transmission density of 0.7 or more, and the three silver halide emulsion layers having different color sensitivities are all directly positive halogenated. By what is a silver emulsion,
It has been found that the above objectives are achieved. The support of the present invention has a transmission density of 0.7 or more. As a result, the thickness of the support is 80-150I! m, but
A direct positive silver halide light-sensitive material with good sharpness can be obtained. The support used in the present invention uses paper as the base, for example,
It is possible to use a structure in which a first layer is formed by a coating layer such as a white polyethylene layer on the silver halide emulsion side of both sides of the inner paper layer, and a transparent polyethylene layer is formed on the opposite side. In this case, it is preferable that the first layer containing a white filler and the like on the emulsion side of the support has a transmission density of 0.25 or more. Further, the thickness of the first layer is preferably 20 μm or more. Further, the white filler is preferably 10% or more, more preferably 13% or more, based on the entire polyethylene containing the filler. The transmission density of the entire support is required to be 0.7 or more, but the sum of the transmission density of each layer is not necessarily 0. For example, when a reflective support is used, the total support is selected depending on the desired properties. Although various materials can be used as desired, for example, reflective supports having a water-resistant surface such as polyolefin laminate, synthetic paper, etc. are preferably used. A water-resistant surface can be formed by coating a substrate, such as a paper substrate, with a hydrophobic resin, and such a hydrophobic resin coating layer is formed on both sides of the photosensitive material so that the first layer and the transparent opposite side thereof are coated with a hydrophobic resin coating layer. layers can be provided. In an embodiment in which such a water-resistant surface is formed, even when the silver halide photographic light-sensitive material is immersed in a bath used for development processing, it is possible to prevent water from forming on the substrate. Examples of resins used for the hydrophobic resin coating layer (transparent layer) coated on the back surface include polyolefins such as polyethylene, polypropylene, and polybutene, olefins such as ethylene, propylene, and butene, and vinyl acetate, vinylidene chloride, and maleic anhydride. Copolymers with monomers such as acids (e.g. ethylene-vinyl acetate copolymer, propylene-vinylidene chloride copolymer, propylene-vinylidene chloride copolymer)
(maleic anhydride copolymer, etc.), homopolymers or copolymers of polystyrene, polyvinyl chloride, polyacrylate, saturated polyester, polycarbonate, etc., or blends thereof. The thickness of this hydrophobic resin coating layer is not particularly limited, but is generally preferably about 15 to 50 μm. Further, the hydrophobic resin layer (first 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-olefins such as propylene and butene-1, styrene, vinyl compounds such as vinyl stearate, vinyl acetate, acrylic acid, methacrylic acid, and acrylamide, and methyl acrylate. , esters of vinyl carboxylic acid compounds such as ethyl acrylate, methyl methacrylate, and ethyl methacrylate, metal salts of acrylic acid and methacrylic acid, and diene compounds such as butadiene and isoprene. There is no particular restriction on the molecular weight of polyethylene resin as long as extrusion coating is possible, but it usually has a molecular weight of 20.
,000 to 200,000 is used. Further, 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 types. Various coatings can be used to apply such a hydrophobic resin onto, for example, a paper substrate to form a hydrophobic resin coating. Particularly common coating methods include extrusion coating methods. 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, calcium sulfate, etc. can be added to sharpen the image. These substances may be used alone or in combination of two or more, for example, in an amount of about 5 to 2 parts by weight per 100 parts by weight of the resin.
It can be added in an amount of 5 parts by weight. Such an opaque layer can be provided, for example, on the surface of the support. When using such a hydrophobic resin layer containing a light-reflecting substance, there is no need to coat it with a baryta layer or the like to impart reflectivity even when a paper base is used. The photographic light-sensitive material of the present invention is provided with a red-sensitive direct positive silver halide emulsion layer containing a cyan coupler and a green-sensitive direct positive silver halide emulsion layer containing a magenta coupler on a support having a thickness of 80 to 150 μm. Depending on the color scheme, a yellow filter layer and a blue-sensitive direct positive silver halide emulsion layer containing a yellow coupler are constructed. These layers may be formed by coating in the above-mentioned order sequentially from the support side. The yellow dye-forming couplers contained in each of the above color-sensitive layers are benzoylacetanilide type, pivaloylacetanilide type, or a so-called split-off group in which the carbon atom at the coupling position can be detached during coupling. Substituted two-equivalent type yellow couplers and the like are useful. As the magenta dye-forming coupler, a 5-pyrazolone type, pyrazolotriazole type, pyrazolinobenzimidazole type, indasilone type, or a two-equivalent type magenta coupler having a sprint-off group is used. In addition, cyan dye-forming couplers include phenolic,
Useful are naphthol type, vilazoquinazolone type, or two-equivalent type cyan couplers having a split-off group. These dye-forming couplers can be selected arbitrarily, and there are no particular limitations on how they are used, how much they are used, etc. In addition, in order to prevent color fading of the dye image due to short-wavelength actinic rays, an ultraviolet absorber can be used, such as thiazolidone, benzotriazole, acrylonitrile, benzophenone compounds, etc. In particular, Tinubi 7PS,
12o, 32o, 326, 327, 328 (
Both products (manufactured by Ciba Geigy) are advantageous to use alone or in combination. When carrying out the present invention, in addition to the four layers of the above-mentioned boundary, green and blue color-sensitive layers, and one yellow filter layer, a protective layer, an intermediate gelatin layer, or an antihalation layer underneath may be formed as necessary. Good too. As the direct positive image forming silver halide emulsion used in the light-sensitive material of the present invention, for example, an internal latent image type silver halide emulsion can be used. For example, U.S. Patent 2.592.25
The so-called conversion type silver halide emulsion by the conversion method described in No. 0, or U.S. Pat. No. 3,206,3
No. 16, No. 3.317, 322 and No. 3.367.7
No. 78, silver halide emulsions with internally chemically sensitized silver halide grains, or U.S. Pat.
271,157, 3,447.927 and 3,
Silver halide emulsions having silver halide grains incorporating polyvalent metal ions as described in US Pat. No. 531,291 or halogenated emulsions containing dopants as described in U.S. Pat. Silver halide emulsion with weakly chemically sensitized silver grain surfaces, or JP-A-1987-
No. 8524, No. 50-38525 and No. 53-240
So-called core-shell type silver halide emulsions produced by the lamination method described in No. 8, and other JP-A-52-156614
Silver halide emulsions described in Japanese Patent No. 55-127549 and Japanese Patent No. 57-79940 can be used. In this case, it is particularly preferable that the internal latent image type silver halide be made of layered grains. Such silver halide can be produced in the same manner as ordinary laminated silver halide. For example, Japanese Patent Application Publication No. 1973-
No. 8524, No. 50-38525, No. 53-6022
No. 2, No. 55-1524 and U.S. Patent No. 3,206.3
As described in No. 13, etc., silver chloride grains are formed, bromide is added to convert them into silver bromide grains, and a halide is further added to silver nitrate to form a layer, or silver iodobromide grains are formed with less excess halogen. Examples include a method in which silver chloride and silver bromide are sequentially laminated. The composition of the silver halide grains inside the laminated type and core-shell type has a high silver bromide content (60-100 mol%)
Silver iodobromide grains are suitable. The composition of the silver halide layered on the outside is preferably silver chlorobromide, and from the viewpoint of developability, it is desirable to have a high silver chloride ratio (70 mol % or more). The grain size of silver halide is 0.2 to 1.7
Particles of μ can be used, and when high contrast is required, those with a narrow particle size distribution are preferable, and when low contrast is required, those with a wide particle size distribution are preferable. Various photographic additives can be added to the internal latent image type silver halide emulsion. For example, optical sensitizers that can be used include cyanines, merocyanines, trinuclear or tetranuclear merocyanines, trinuclear or tetranuclear cyanines, styryls, holoporacyanines, hemicyanines, oxonols, and hemioxonols. Examples include nols and the like. Internal latent image type silver halide emulsions can be supersensitized. Regarding the method of super-sensitization, see, for example, "Review of the mechanism of super-sensitization".
tization) Photographic Science and Engineering (Photogra
phicScience and Engineering
ng) (PSE) Vol, I8゜4th
418 (1974). When internal latent image type silver halide emulsions are used, the emulsions contain stabilizers that are commonly used, such as compounds with azaindene rings, in order to keep the surface sensitivity as low as possible and to give lower minimum density and more stable properties. and a heterocyclic compound having a mercapto group. As the compound having an azaindene ring, for example, 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene is preferable. Among the heterocyclic compounds in which the mercapto group is a nitrogen-containing heterocyclic compound, a pyrazole ring, 1.
2. 4-) riazole ring, 1.2.3-triazole ring, 1.3.4-thiadiazole ring, 1.2.3-thiadiazole ring, 1,2.4-thiadiazole ring, l,
2゜5-thiadiazole ring, 1.2,3.4-tetrazole ring, pyridazine ring, 1. 2. 3-1-riazine ring, 1.2.4-triazine ring, 1.3.5-triazine ring, etc., and rings in which 2 to 3 of these rings are condensed, such as triazolotriazole ring, diazaindene ring, triazine Examples include a denene ring, a tetrazaindene ring, a pentazaindene ring, a phthalazinone ring, an indazole ring, etc., and 1-phenyl-5-mercaptotetrazole is particularly preferred. In addition, wetting agents are used depending on the purpose, examples of which include dihydroxyalkanes,
Furthermore, as a film property improver, for example, a copolymer of alkyl acrylate or alkyl methacrylate and acrylic acid or methacrylic acid, a styrene-maleic acid copolymer, a styrene-maleic anhydride half alkyl ester copolymer, etc. can be used by emulsion polymerization. The resulting water-dispersible particulate polymeric substances are suitable, and examples of coating aids include saponin, polyethylene glycol, lauryl ether, and the like. Other photographic additives include gelatin plasticizers, surfactants, ultraviolet absorbers,
It is optional to use H adjusters, antioxidants, antistatic agents, thickeners, graininess improvers, dyes, mordants, brighteners, development speed regulators, matting agents, anti-irradiation dyes, etc. be. The silver halide photographic material of the present invention may contain appropriate gelatin (including oxidized gelatin) and its derivatives depending on the purpose. Preferred gelatin derivatives include, for example, acylated gelatin, guanidylated gelatin, carbamylated gelatin, cyanoethanolated gelatin, and esterified gelatin. Furthermore, in the silver halide photographic material of the present invention,
In addition to gelatin, other hydrophilic binders can be included in the hydrophilic colloid layer. This hydrophilic binder can be added to photographic constituent layers such as an emulsion layer, an intermediate layer, a protective layer, a filter layer, and a backing layer depending on the purpose. It is possible to contain agents, lubricants, etc. Further, the photographic constituent layers of the light-sensitive material of the present invention can be hardened with any suitable hardening agent. Preferred hardening agents include chromium salts, zirconium salts, aldehyde hardeners such as formaldehyde and mucohalogen acids, halotriazine hardeners, polyepoxy compounds, ethyleneimine hardeners, vinyl sulfone hardeners, and acryloyl hardeners. It will be done. The silver halide photographic light-sensitive material of the present invention also has an emulsion layer on a support, and as described above, if necessary, a filter layer, an intermediate layer, a protective layer, a subbing layer, a backing layer, an antihalation layer, etc. It is manufactured by coating various photographic constituent layers. As a coating method, dip coating, air doctor coating, extrusion coating, slide hopper coating, curtain flow coating, etc. can be used. In the present invention, when directly forming a positive image using an internal latent image type silver halide photographic light-sensitive material, the main step is to transfer the internal latent image type silver halide photographic light-sensitive material, which has not been fogged in advance, to the internal latent image type silver halide photographic light-sensitive material after image exposure. It is common to perform surface development after capri treatment or while performing fog treatment. The fogging treatment can be carried out by providing uniform exposure over the entire surface or by using a capricant. In this case, uniform exposure over the entire surface is preferably carried out by immersing or moistening the image-exposed internal latent image type silver halide photographic light-sensitive material in a developer or other aqueous solution, and then uniformly exposing the entire surface. . The light source used here may be any light within the sensitive wavelength range of the internal latent image type silver halide photographic light-sensitive material, and it is also possible to irradiate with high-intensity light such as flash light for a short time, or with a weak Light may be irradiated for a long time. The time for uniform exposure over the entire surface can be varied over a wide range depending on the internal latent image type silver halide photographic light-sensitive material, the processing conditions, the type of light source used, etc. so as to ultimately obtain the best positive image. Further, a wide variety of compounds can be used as the above-mentioned capri agent, and the capri agent only needs to be present during development, for example, in an internal latent image type silver halide photographic light-sensitive material such as a silver halide emulsion layer, or Although it may be contained in a developing solution or a processing solution prior to development, it is preferably contained in an internal latent image type silver halide photographic light-sensitive material (particularly preferably in a silver halide emulsion layer). The amount used can vary widely depending on the purpose, and the preferable amount is 1 to 150 per mole of silver halide when added to a silver halide emulsion layer.
0aw, particularly preferably 1O to 1000■. Further, when added to a processing solution such as a developer, the preferable addition amount is 0.01 to 5 g/It, particularly preferably 0.0
8~0.15g/j! It is. Such fogging agents include, for example, US Pat. Nos. 2,563,785 and 2,588.
．． 982, or the hydrazines described in U.S. Pat. No. 3,227,552,
or hydrazone compounds: also U.S. Patent 3.615,6
No. 15, No. 3,718,470, No. 3,719.49
No. 4, No. 3,734.738 and No. 3,759,90
Examples include heterocyclic 4'I&nitrogen compounds described in No. 1, etc.; and acylhydrazinophenylthioureas described in U.S. Pat. No. 4,030.925. Further, these fogging agents can also be used in combination. For example, Research Disclosure + - (Re5search Dis
Closure) No. 15162 describes the use of a non-adsorption type fogging agent in combination with an adsorption type fogging agent, which can also be applied 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 include hydrazine compounds such as -methylsulfonyl-2-(3-phenylsulfonamidophenyl)hydrazine and formaldehyde phenylhydrazine. 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 exposing the entire surface of the material after image exposure or developing it in the presence of a fogging agent. Any developing method may be employed as the developing method for the photosensitive material, preferably a surface developing method. This surface development processing method means processing with a developer substantially free of silver halide solvent. In carrying out the present invention, a positive image (developed image) corresponding to the original image can be formed by subjecting the exposed silver halide photographic material to processing using a processing solution having development processing and fixing ability. The above-mentioned development processing includes, in addition to color development processing, a combination of black-and-white development and color development, such as in reversal color processing. It also includes full-surface exposure or development in the presence of a fogging agent, such as in the processing of internal latent image type silver halide photographic materials. The primary aromatic amino color developer used in the color development process of the present invention includes various types that are widely used in various color photographic processes. These developers include aminophenol and p-phenylenediamine derivatives. Since these compounds are more stable in the free state, they are generally used in the form of salts, such as hydrochlorides or sulfates. Further, these compounds are generally used at a concentration of about 0.1 g to about 30 g for the color developer 11;
More preferably, about 1 g to about 1 g for the color developer 11
Use at a concentration of 5g. Examples of aminophenol-based developers include 0-aminophenol, p-aminophenol, and 5-amino-2-
Included are oxy-toluene, 2-amino-3-oxy-toluene, 2-oxy-3-amino-1,4-dimethyl-benzene, and the like. A particularly useful primary aromatic amino color developer is N. It is an N-dialkyl-p-phenylenediamine compound, and the alkyl group and phenyl group may be substituted or unsubstituted. Among them, particularly useful compound examples 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-hydroxyethyl Aminoaniline, 4-amino-methyl-N. N-diethylaniline, 4-amino-N-(2-methoxyethyl)-N-ethyl-3-methylaniline-p-)
Examples include luenesulfonate. In addition to the first aromatic amino color developer, the alkaline color developer that can be used in the present invention further contains various components that are normally added to color developers, such as sodium hydroxide, sodium carbonate, and potassium carbonate. It may optionally contain alkaline agents such as alkali metal bisulfites, alkali metal thiocyanates, alkali metal % halides, benzyl alcohol, water softeners, thickening agents, and the like. The pH value of this color developer is usually 7 or higher, most commonly about 10 to about 13. The fixing solution used in carrying out the present invention is a processing solution containing a soluble complexing agent that is solubilized as a silver halide complex salt, and includes not only a general fixing solution but also a bleach-fixing solution, a single-bath development fixing solution, - Bath development bleach-fix solutions are also included, but bleach-fix solutions are preferred. Soluble complexing agents include, for example, thiosulfates such as potassium thiosulfate, sodium thiosulfate, ammonium thiosulfate, thiocyanates such as potassium thiocyanate, sodium thiocyanate, ammonium thiocyanate, or thioureas, thioethers, Typical examples include bromide and iodide, but the inclusion of thiosulfate in particular improves the stability of dye images over time, chemical stability, and ability to form soluble complexes with silver halide. desirable. After color development processing, processing is performed with a processing liquid having fixing ability. In color processing, if the processing liquid having fixing ability is a fixing liquid, bleaching processing is performed before that. A metal complex salt of an organic acid is used as a bleaching agent in the bleach solution or bleach-fix solution used in the bleaching process, and the metal complex salt oxidizes metallic silver produced by development and converts it into silver halide. It has the effect of coloring the uncolored part of the coloring agent, and its structure is that metal ions such as iron, cobalt, copper, etc. are coordinated with aminopolycarboxylic acid or organic acids such as oxalic acid and citric acid. The most preferred organic acids used to form such metal complexes include polycarboxylic acids and aminopolycarboxylic acids. These polycarboxylic acids or aminopolycarboxylic acids may be alkali metal salts, ammonium salts or water-soluble amine salts. Specific representative examples of these include the following. [1] Ethylenediaminetetraacetic acid [2] Diethylenetriaminepentaacetic acid [3] Ethylenediamine-N-(β-oxyethyl)-N, N', N'
-) Solacetic acid [4] Propylenediaminetetraacetic acid [5] Nitrilotriacetic acid [6] Cyclohexanediaminetetraacetic acid [7] Iminodiacetic acid [8] Dihydroxyethylglycincitric acid (or tartaric acid)

[9] Ethyl ether diamine tetraacetic acid [10] Glycol ether diamine tetraacetic acid [11] Ethylene diamine tetrapropionic acid [12] Phenyl diamine tetra acetic acid [13] Ethylene diamine tetra acetic acid disodium salt [14] Ethylene diamine tetra acetate tetra(trimethylammonium) ) Salt [15] Ethylenediaminetetraacetic acid tetrasodium salt [16] Diethylenetriaminepentaacetic acid pentasodium salt [17] Ethylenediamine-N-(β-oxyethyl)
-N, N', N'-) Sodium acetate salt [18] Propylenediaminetetraacetic acid sodium salt [19] Nitrilotriacetic acid sodium salt [20] Cyclohexanediaminetetraacetic acid sodium salt The bleaching solution used is as described above. In addition to containing a metal complex salt of an organic acid as a bleaching agent, it can also contain various additives. As additives, it is particularly desirable to include rehalogenating agents such as alkali halides or ammonium halides, such as potassium bromide, sodium bromide, sodium chloride, and ammonium bromide, metal salts, chelating agents, and the like. Additionally, pH buffering agents such as borates, oxalates, acetates, carbonates, and phosphates, alkylamines, polyethylene oxides, and other substances known to be added to ordinary bleaching solutions may be added as appropriate. . Furthermore, the fixing solution and bleach-fixing solution contain sulfites such as ammonium sulfite, potassium sulfite, ammonium bisulfite, potassium bisulfite, sodium bisulfite, ammonium metabisulfite, potassium metabisulfite, and IJum. pH buffering agents consisting of various salts such as boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, ammonium hydroxide, etc. alone or in combination. or more. When processing is carried out while replenishing the bleach-fixing solution (bath) with a bleach-fixing replenisher, the bleach-fixing solution (bath) may contain thiosulfate, thiocyanate, sulfite, etc. The processing solution (
(bath) may be refilled. In order to increase the activity of the bleach-fix solution, air or oxygen may be blown into the bleach-fix bath and the bleach-fix replenisher storage tank, if desired, or a suitable oxidizing agent, such as peroxide, may be added. Hydrogen, bromate, persulfate, etc. may be added as appropriate. After treatment with a treatment liquid having a fixing ability, a normal water washing treatment may be performed, but particularly when carrying out the present invention, it is preferable to perform a stabilization treatment that does not substantially require a step after water washing. Stabilization treatment that does not substantially include a water rinsing process refers to stabilization treatment using a single-tank or multiple-tank countercurrent method immediately after treatment with a treatment liquid that has fixing ability, but does not include rinsing treatment or supplementary treatment. Processing steps other than general water washing, such as water washing and a known water washing accelerator bath, may also be included. In the stabilization treatment process, the method of bringing the stabilizing solution into contact with the silver halide photosensitive material is preferably to immerse the silver halide photographic material in the bath in the same way as with general processing solutions. It may be applied to the emulsion surface of the silver halide photographic material, both sides of the conveyor leader, and the conveyor belt by means of a spray method or the like. The case where a stabilizing bath by the immersion method is used will be mainly explained below. It is preferable that the stabilizing liquid contains a chelating agent having a chelate stability constant of 6 or more with respect to iron ions. 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, polyhydroxy compounds, and the like. The term "ferrous ion" refers to ferric ion (Fe"). Specific examples of chelating agents having a chelate stability constant of 6 or more with ferric ion include diethylenetriaminepentaacetic acid, nitrilotriacetate, Examples include acetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, etc. The amount of the above chelating agent used is 0.01 per stabilizing liquid If.
~50g 1, preferably 0.05~20g. Furthermore, preferred compounds to be added to the stabilizing solution include:
Examples include anti-spill agents, water-soluble metal salts, ammonium compounds, and the like. Examples of the above-mentioned anti-spill agents include isothiazoline-based, benzisothiazoline-based, thiapendazole-based, and the like. Furthermore, examples of metal salts include Ba, Ca, and Ce. Co + In, La + Mn r Ni, P
b + Sn. Zn, Ti, Zr, Mg, A1. is a metal salt of Sr,
halides, hydroxides, sulfates, carbonates, phosphates,
It can be supplied as an inorganic salt such as acetate or as a water-soluble chelating agent. The amount used is I x 10 per 1e of stabilizing liquid.
-' to I X 10-' mol, preferably 4XIO-' to 2
The range is from X I O-' to I
It is in the range of 0g. In addition to the above-mentioned compounds, the stabilizing liquid also contains a fluorescent whitening agent, an organic sulfur compound, an onium salt, a hardening agent, a quaternary salt, a polyethylene oxide derivative, a siloxane derivative, and other water droplet prevention agents.
pHtJt buffering agents such as boric acid, citric acid, phosphoric acid, acetic acid, or sodium hydroxide, sodium acetate, potassium citrate, organic solvents such as methanol, ethanol, dimethyl sulfoxide, dispersants such as ethylene glycol, polyethylene glycol, etc. It is optional to add various additives to improve and extend the processing effect, such as color sub-regulators. The above compounds and other additives can be added to the stabilization tank as a concentrated liquid, or the above compounds and other additives may be added to the stabilizing liquid supplied to the stabilization tank and then stabilized. There are various methods, such as using it as a supply solution for the stabilizing solution, or adding it to the pre-bath of the stabilization treatment process and making it present in the stabilization bath after being included in the silver halide photographic material. It may be added by such an addition method. As for the method of supplying the stabilizing liquid in the stabilization treatment step, when a multi-tank countercurrent system is used, it is preferable to supply the stabilizing liquid to the rear bath and overflow from the front bath. The pH value of the treatment liquid in the stabilizing bath is preferably in the range of pH 4 to 8. Further, the pH can be adjusted using the pH1JI adjuster described above. The treatment temperature during the stabilization treatment is, for example, 20°C to 50°C.
℃, preferably in the range of 25°C to 40°C. In addition, from the viewpoint of rapid processing, a short treatment time is preferable, but it is usually 20 seconds to 5 minutes, most preferably 30 seconds to 2 minutes. It is preferable that the treatment time in the latter stage tank is long. When carrying out the present invention, washing with water may not be necessary before and after the stabilization treatment, but surface cleaning with a sponge, rinsing with a small amount of water within a short period of time, image stabilization, and silver halide photographic material may be carried out. It is optional to provide a treatment tank for adjusting the surface properties of the material. Examples of agents for stabilizing the image and adjusting the surface properties of the silver halide photographic material include activators such as formalin and its derivatives, siloxane derivatives, polyethylene oxide compounds, and quaternary salts. In carrying out the present invention, it is optional to provide additional processing steps in addition to the processing steps described above. Furthermore, silver may be recovered by a known method not only from the above-mentioned stabilizing solution but also from a processing solution containing a soluble silver complex salt such as a fixing solution or a bleach-fixing solution. In addition, if the above-mentioned stabilization treatment is performed, the washing process is virtually unnecessary, so there is no need for piping equipment for washing.
This has the advantage that the device itself can be easily installed at any location. [Examples] Examples of the present invention will be described in detail below, but the present invention is not limited to these embodiments. Each emulsion was prepared as follows, and a sample of a silver halide photographic light-sensitive material was manufactured. Preparation of emulsion S 2.0% inert gelatin solution 750mj! While maintaining the temperature at 50° C., the following Al solution and B solution were added at the same time while stirring and injected over 3 minutes. After aging for 25 minutes, excess salt was removed by precipitation and washing with water, and the mixture was redispersed, and liquid C1 and liquid D1 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 750 m6 of 1.5% inert gelatin solution was kept at 60''C, and while stirring, the following solutions A2 and B were simultaneously added and injected over 15 minutes. After aging for 40 minutes, the excess was removed by the precipitation washing method. After removing the salt, the mixture was redispersed, Hypo 10■ was added, and then liquid C2 and liquid D2 were added.After 10 minutes, excess water-soluble salt was removed again, and a small amount of gelatin was added to disperse the halogenated root particles. Preparation of Emulsion M 750 ml of 2.0% inert gelatin solution was kept at 50°C.
While stirring, the following solutions A3 and B were simultaneously added and injected over 5 minutes. After aging for 25 minutes, excess salt was removed by precipitation and washing with water, followed by redispersion, and liquid C1 and liquid D2 were added. 10
After a few minutes, the excess water-soluble salt was removed again, and a small amount of gelatin was added to disperse the silver halide grains. A 1-night A2 solution A3 solution B solution C1 solution C2 solution D 1-night D2 solution Add sensitizing dyes, couplers, etc. to these three emulsions as shown below, and coat on the support described later Multilayer color sensitization Created the material. Red-sensitive emulsion layer (first layer) For emulsion S and emulsion M, sensitizing dye [D-3],
CD-4), stabilizer (T-1), (T-2), surfactant (S-2), further dibutyl phthalate, ethyl acetate,
Surfactant (S-2), 2゜5-dioctylhydroquinone and cyan coupler CCC-1), (CC-23
A coupler solution containing Protect Protect was added. Gelatin was added and coated so that the mixing ratio of each emulsion was 4=6 (weight ratio): Emulsion M: Emulsion S. First intermediate layer (second layer) A gelatin solution containing a protect-dispersed solution containing dioctyl phthalate, 2,5-dioctylhydroquinone ultraviolet absorber Tinuvin 328 (manufactured by Ciba Geigy), and a surfactant (S-1:l). Prepared tinuvin application io, 15
g/n? A green-sensitive emulsion layer (third layer) is coated so that sensitizing dye CD-2) and stabilizer (T
-1), CT-2], surfactant C5-2], and further contains dibutyl phthalate, ethyl acetate, 2゜5~dioctylhydroquinone, surfactant [S-1], and magenta coupler [MC-1]. The dispersed coupler solution was added. Gelatin was added, and then a hardening agent (H-1) was added, and the coating was applied so that the ratio of emulsion M to emulsion S was 4=6 (weight ratio). 2nd intermediate layer (4th layer) The same formulation as the 1st intermediate layer with a coating amount of Tinuvin 328 of 0.2
Apply to g/rd. Yellow filter layer 1 (5th layer) 1 layer of yellow colloid made by oxidation in an alkaline weak reducing agent (the weak reducing agent was removed by the noodle water washing method after neutralization), dioctyl lephrate, ethyl acetate, surfactant ( S-1), 2.5-di, octylhydroquinone solution, surfactant (S-2) and hardener (H-1) were added so that the colloid coating amount was 0.1.5 g/m. 3rd intermediate layer (6th layer) Same as the 1st intermediate layer. Blue-sensitive emulsion layer (7th layer) Emulsion is made, and sensitizing dye (D-1) and stabilizer ( T-1), (T-3), surfactant (S'-2)
Further, a protected dispersed coupler solution containing dibutyl phthalate, ethyl acetate, 2,5-dioctylhydroquinone, surfactant (S-1) and yellow coupler CYC-1 was added. Add gelatin and hardener [Hl] to make emulsion L.
: Emulsion M was mixed and coated at a ratio of 5:5 (weight ratio). 3rd intermediate layer (8th layer) Apply Tinuvin 328 in the same formulation as the 1st intermediate layer at a coating amount of 0.3
Apply so that it becomes 5g/rrr. Protective layer (9th layer) Colloidal silica, coating aid (S-2), hardener (H-
2) Using gelatin liquid containing CH-3), gelatin coating amount is 1.0 g/rr? Apply it so that Low-density polyethylene containing white titanium oxide and having a density of 0.92 was extruded at 310° C. to form a layer of 22 μm thick, and coated onto a medium paper having a thickness of 70 μm and a transmission density of 0.64. Further, on the other side, high-density polyethylene with a density of 0.96 was extruded at 330° C. to form a layer of 25 μm in thickness to obtain a laminated paper. Five types of supports ~E were prepared by changing the content of white titanium oxide as shown in Tube 1 below. The first layer to the ninth layer were coated on the support by a simultaneous coating method and dried to prepare a sample. Hereafter, the remaining 3M public] [D-1) CD-2) CD-3) (D-4] rT-1) [T-2]H (S-1) C2I+ 5 (H-2) (H-3 ] [MC-1) (CC-1) (CC-2) The obtained samples were tested using the image forming apparatus shown in FIGS. 1 and 2. Note that FIG. 1 is a schematic cross-sectional view showing an example of an image forming apparatus that can use the photosensitive material of the present invention.
, a conveying section 13, a photo processing section 24, and a drying section 30. The image exposure section 3 includes a light source 4, a first reflective mirror 5, a second reflective mirror 6, a third reflective mirror 7, a lens 8, a fourth reflective mirror 9, and a first reflective mirror 5O. The light source 4 is provided with a slit, and a light source with no uneven light distribution particularly in the axial direction is preferably used. In this embodiment, a rod-shaped halogen lamp (200W) with a slit width of 10i1 is used, and a ground glass is provided on the light exit surface to eliminate uneven light distribution. Original image placed on transparent platen glass 2 (not shown)
is subjected to slit exposure by the light source 4, and as the light source 4 scans, the reflected light from the original screen, that is, the optical image, is reflected by the first reflecting mirror 5, the second reflecting mirror 6, the third reflecting mirror 7, the lens 8, and the fourth reflecting mirror 9. The silver halide photographic material 12, which is moving in synchronization with the scanning movement of the light source 4, is sequentially exposed through the exposure aperture 23 via the fifth reflecting mirror 10. In this way, a light image corresponding to the original image is exposed onto the silver halide photographic light-sensitive material 12. In addition, the first reflecting mirror 5,
The second reflecting mirror 6 and the third reflecting mirror 7 move along with the scanning movement of the light a4. In addition, the lens 8, the fourth reflecting mirror 9, and the fifth reflecting mirror 10 are stationary during exposure, but in order to change the optical distance when changing magnification, they are moved to predetermined positions corresponding to the changing magnification before exposure. Moving. On the other hand, the silver halide photographic material 12, which is a sample according to this example, is formed into a roll and is stored in a dark box I2'. The silver halide photographic material 12 pulled out from the dark box 12' is pressed against a series of rotating roller pairs 14.1.
4' to 21 and 21' are transported within the transport section 13. By the way, the silver halide photographic light-sensitive material 12, which has hitherto been in the form of a roll, is cut by a cutting member 22 provided in the transport path.
is cut to the desired size. Therefore, after being cut, the silver halide photographic material 12 is conveyed in the form of a sheet. The cutting member 22 may be one in which the cutter blade cuts the silver halide photographic light-sensitive material 12 while moving in the width direction, or one in which the cutter blade descends horizontally with respect to the surface of the silver halide photographic light-sensitive material 12. Various materials can be used, such as one that cuts the silver halide photographic material 12 at once, but there is no particular limitation as long as the material can cut the silver halide photographic material 12. Of course, the silver halide photographic light-sensitive material 12 may be in the form of a sheet instead of a roll. When a sheet-like material is used, the cutting member 22 does not need to be provided. The silver halide photographic material 12 cut into sheets in this way is
As described above, the light image of the original image is exposed at the exposure port 23 while moving in synchronization with the scanning movement of the light source 4. In this embodiment, the silver halide photographic material 12 is cut before exposure, but it may be cut after exposure. The exposed silver halide photographic material 12 is then sent to a photographic processing section 24. The photographic processing section 24 subjects the exposed silver halide photographic light-sensitive material 12 to photographic processing to form a developed image corresponding to the original image. In this embodiment, the photographic processing section 24 includes four processing tanks, namely a developing processing tank 25, a bleaching and fixing processing tank 26, and a stabilizing tank 27, 28. Stabilization tank 27.2
8 is a two-tank countercurrent system. Further, the light source 29 is for providing fog exposure during development processing when, for example, an internal latent image type silver halide photographic material is used as the silver halide photographic material 12. In the photographic processing section 24, the exposed silver halide photographic material 12 is processed for a predetermined time in each processing tank, then sent to the drying section 3o, dried, and discharged from the apparatus. In the figure, 31 is a waste liquid storage section, and 32 is a replenishment liquid storage section. (Although the present embodiment has a configuration of five mirrors, the image exposure unit 3 can also be made more compact by having three or one mirror, for example). Using the above apparatus, the prepared sample is tested as a light-sensitive material, and a sharpness test is performed. That is, a rectangular chart of three pieces/dragon is placed on a document table, samples A to E using each support provided with a photosensitive layer are loaded into a dark box (magazine) 12', and transported.
Exposure and development were performed. That is, from a rectangular exposure slit (window) of 1 x 20 cm.
Scanning exposure was performed at a constant speed of cna/second, and after exposure, the following photographic processing was performed. Processing steps (processing temperature and processing time) [1] Immersion (color developer) 38°C 8 seconds [2] Capri exposure -1 lux for 10 seconds [3] Color development 38°C 2 minutes [4] Bleach-fixing 35°C60 Seconds [5] Stabilization processing
25~30'C 1 minute 30 seconds (6) Drying 75~
8o°c 1 minute processing solution composition (color developer) Benzyl alcohol 10+yl ethylene glycol 15njl! Potassium sulfite 2.0g Potassium bromide 1.5g Sodium chloride
0.2g potassium carbonate
30.0 g hydroxylamine sulfate 3.0 g polyphosphoric acid (TPPS)
2.5g 3-Methyl-4-amino-N-ethyl-N-(β-methanesulfonamidoethyl)-aniline sulfate 5.5g Fluorescent brightener (4,4'-diaminostilbenzsulfonic acid derivative) 1 .0g potassium hydroxide
Add 2.0g water and total amount is 17! Binding, pH
Adjust to 10,20. (Bleach-fix solution) Ethylenediaminetetraacetic acid diammonium dihydrate 60g Ethylenediaminetetraacetic acid M 3g Ammonium thiosulfate (70%) 100+n7! Ammonium sulfite (40%?8' (FIL) 27.5 ml Adjust the pH to 7.1 with potassium carbonate or glacial acetic acid, and add water to bring the total volume to 11. (Stabilizing solution) 5-chloro-2-methyl- 4-Isothiazolin-3-one 1.0g Ethylene glycol 10g 1-Hydroxyethylidene-1,1'-diphosphonic acid 2.5g Bismuth chloride 0.2g Magnesium chloride 0.1g Ammonium hydroxide (28% water soluble?&) 2.0g Add 1.0 g of sodium nitrilotriacetate water to bring the total volume to 11, and adjust the pH to 7.0 with ammonium hydroxide or sulfuric acid.The stabilization treatment was performed using a countercurrent method in a two-tank configuration as described above.Photosensitive material The line of the rectangular chart reproduced above is the Sakura Microdensitometer PDM-5 (Konishiroku Photo Industry).
Co., Ltd.), and the contrast was compared to evaluate the sharpness. The results are shown in Table 1. The larger the contrast, the higher the sharpness. Table 1 (PE stands for polyethylene) *The transmission density of all layers does not match the sum of the transmission density of the white PE layer, inner paper layer, and transparent PE layer. As is clear from Table 1, the contrast ratios of comparative samples using supports A and E, which have transmission densities of 0, 65, and 0.68, which are lower than 0.7, are 0.21 and 0.36, respectively. However, the transmission density is 0.79.0.84.0.8 with a transmission density of 0.7 or more.
The samples of the present invention using supports B, C, and D, each having a contrast ratio of 0.64. Q, 70.0.74, which is high, indicating excellent sharpness. In this way, although the support of the sample of the present invention is as thin as 117μ,
It shows excellent sharpness. [Effects of the Invention] As described above, the silver halide photographic light-sensitive material for direct positive image formation of the present invention has the effect of being able to reduce the thickness, suppressing a decrease in sharpness, and being excellent in practicality. .

[Brief explanation of drawings]

FIG. 1 is a schematic sectional view showing an example of an image forming apparatus that can use the photosensitive material of the present invention. FIG. 2 is a partially enlarged view. 1... Image forming apparatus main body, 3... Image exposure section, 11
...Paper feeding section, 12 Photosensitive material (sample), 13... Conveying section, 22... Cutting member, 24... Photographic processing section, 3o
...Drying section. Patent applicant: Konishiroku Photo Industry Co., Ltd. Patent attorney Toru Takatsuki Figure 1 Figure 2

Claims (1)

[Claims] A silver halide photographic material having three silver halide emulsion layers having different color sensitivities containing a cyan coupler, a magenta coupler and a yellow coupler on a support, the support having a thickness of 80 to 150 μm. silver halide for direct positive image formation, which has a transmission density of 0.7 or more, and wherein the three silver halide emulsion layers having different color sensitivities are all direct positive silver halide emulsions. Photographic material.